Polymerization of olefins

ABSTRACT

Selected olefins such as ethylene and α-olefins are polymerized by nickel [II] complexes of certain monoanionic ligands. The polyolefins are useful in many applications such as molding resins, film, fibers and others. Also described are many novel nickel compounds and their precursors, as well a novel ligands.

This application claims the benefit of U.S. Provisional Application No. 60/035,190, filed Jan. 14, 1997. This is a division of application Ser. No. 09/006,536 filed Jan. 13, 1998, now U.S. Pat. No. 6,174,975.

FIELD OF THE INVENTION

Olefins are polymerized by a catalyst system that includes a nickel[II] complexes of selected monoanionic bidentate ligands. Some of these complexes are also novel.

TECHNICAL BACKGROUND

Polymers of ethylene and-other olefins are important items of commerce, and these polymers are used in a myriad of ways, from low molecular weight polyolefins being used as a lubricant and in waxes, to higher molecular weight grades being used for fiber, films, molding resins, elastomers, etc. In most cases, olefins are polymerized using a catalyst, often a transition metal compound or complex. These catalysts vary in cost per unit weight of polymer produced, the structure of the polymer produced, the possible need to remove the catalyst from the polyolefin, the toxicity of the catalyst, etc. Due to the commercial importance of polymerizing olefins, new polymerization catalysts are constantly being sought.

SUMMARY OF THE INVENTION

This invention concerns a process for the polymerization of an olefin selected from one or more of R⁶⁷CH═CH₂, cyclopentene, a styrene, a norbornene or H₂C═CH(CH₂)_(s)CO₂R⁷⁷, comprising, contacting, at a temperature of about −100° C. to about +200° C., R⁶⁷CH═CH₂, cyclopentene, a styrene, a norbornene, or H₂C═CH(CH₂)_(s)CO₂R⁷⁷, optionally a Lewis acid, and a compound of the formula:

wherein:

Ar¹, Ar², Ar⁴, Ar⁵, Ar¹⁰, Ar¹¹, Ar¹² and Ar¹³ are each independently aryl or substituted aryl;

R¹ and R² are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R¹ and R² taken together form a ring, and R³ is hydrogen, hydrocarbyl or substituted hydrocarbyl or R¹, R² and R³ taken together form a ring;

A is a π-allyl or π-benzyl group;

R¹⁰ and R¹⁵ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;

R¹¹, R¹², R¹³, R¹⁴, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R⁵⁰, R⁵¹, R⁵², R⁵³ and R⁵⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group, and provided that any two of these groups vicinal to one another taken together may form a ring;

K is N or CR²⁷;

R²² is hydrocarbyl, substituted hydrocarbyl, —SR¹¹⁷, —OR¹¹⁷, or —NR¹¹⁸ ₂, R²⁴ is hydrogen, a functional group, hydrocarbyl or substituted hydrocarbyl, and R²⁷ is hydrocarbyl or substituted hydrocarbyl, and provided that R²² and R or R²⁴ and R²⁷ taken together may form a ring;

R¹¹⁷ is hydrocarbyl or substituted hydrocarbyl;

each R¹¹⁸ is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;

G and L are both N or G is CR⁵⁷ and L is CR⁵⁵;

R⁵⁵, R⁵⁶ and R⁵⁷ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or any two of R⁵⁵, R⁵⁶ and R⁵⁷ taken together form a ring;

R⁶⁷ is hydrogen, alkyl or substituted alkyl;

R⁷⁷ is hydrocarbyl or substituted hydrocarbyl;

R⁷⁸ is hydrocarbyl or substituted hydrocarbyl;

R⁷⁹, R⁸⁰, R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸ and R⁸⁹ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;

R⁹⁰, R⁹¹, R⁹² and R⁹³ are each independently hydrocarbyl or substituted hydrocarbyl;

R⁹⁴ and R⁹⁵ are each independently hydrocarbyl or substituted hydrocarbyl;

R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;

both of T are S (sulfur) or NH (amino);

each E is N (nitrogen) or CR¹⁰⁸ wherein R¹⁰⁸ is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;

R¹⁰⁰, R¹⁰¹, R¹⁰², R¹⁰³, R¹⁰⁴, R¹⁰⁵, R¹⁰⁶, and R¹⁰⁷ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;

R¹⁰⁹, R¹¹⁰, R¹¹¹, R¹¹², R¹¹³, R¹¹⁴, R¹¹⁵ and R¹¹⁶ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;

s is an integer of 1 or more; and

R²⁸ and R²⁹ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;

and provided that when H₂C═CH(CH₂)_(s)CO₂R⁷⁷ is present, R⁶⁷ CH═CH₂ is also present.

This invention also concerns a process for the polymerization of an olefin selected from one or more of R⁶⁷ CH═CH₂, a styrene, a norbornene or H₂C═CH(CH₂)_(s)CO₂R⁷⁷, comprising, contacting, at a temperature of about −100° C. to about +200° C., R⁶⁷CH═CH₂, cyclopentene, a styrene, a norbornene, or H₂C═CH(CH₂)_(s)CO₂R⁷⁷, optionally a Lewis acid, and a compound of the formula:

wherein:

L¹ is a neutral monodentate ligand which may be displaced by said olefin, and L² is a monoanionic monodentate ligand, or L¹ and L2 taken together are a monoanionic bidentate ligand, provided that said monoanionic monodentate ligand or said monoanionic bidentate ligand may add to said olefin;

Ar¹, Ar², Ar⁴, Ar⁵, Ar¹⁰, Ar¹¹, Ar¹² and Ar¹³ are each independently aryl or substituted aryl;

R¹ and R² are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R¹ and R² taken together form a ring, and R³ is hydrogen, hydrocarbyl or substituted hydrocarbyl or R¹, R² and R³ taken together form a ring;

R¹⁰ and R¹⁵ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;

R¹¹, R¹², R¹³, R¹⁴, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R⁵⁰, R⁵¹, R⁵², R⁵³ and R⁵⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group, and provided that any two of these groups vicinal to one another taken together may form a ring;

K is N or CR²⁷;

R²² is hydrocarbyl, substituted hydrocarbyl, —SR¹¹⁷, —OR¹¹⁷, or —NR¹¹⁸ ₂, R²⁴ is hydrogen, a functional group, hydrocarbyl or substituted hydrocarbyl, and R²⁷ is hydrocarbyl or substituted hydrocarbyl, and provided that R²² and R²⁴ or R²⁴ and R²⁷ taken together may form a ring;

R¹¹⁷ is hydrocarbyl or substituted hydrocarbyl;

each R¹¹⁸ is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;

G and L are both N or G is CR⁵⁷ and L is CR⁵⁵;

R⁵⁵, R⁵⁶ and R⁵⁷ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or any two of R⁵⁵, R⁵⁶ and R⁵⁷ taken together form a ring;

R⁶⁷ is hydrogen, alkyl or substituted alkyl;

R⁷⁷ is hydrocarbyl or substituted hydrocarbyl;

R⁷⁸ is hydrocarbyl or substituted hydrocarbyl;

R⁷⁹, R⁸⁰, R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸ and R⁸⁹ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;

R⁹⁰, R⁹¹, R⁹² and R⁹³ are each independently hydrocarbyl or substituted hydrocarbyl;

R⁹⁴ and R⁹⁵ are each independently hydrocarbyl or substituted hydrocarbyl;

R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;

both of T are S (sulfur) or NH (amino);

each E is N (nitrogen) or CR¹⁰⁸ wherein R¹⁰⁸ is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;

R¹⁰⁰, R¹⁰¹, R¹⁰², R¹⁰³, R¹⁰⁴, R¹⁰⁵, R¹⁰⁶, and R¹⁰⁷ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;

R¹⁰⁹, R¹¹⁰, R¹¹¹, R¹¹², R¹¹³, R¹¹⁴, R¹¹⁵ and R¹¹⁶ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;

s is an integer of 1 or more; and

R²⁸ and R²⁹ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;

and provided that when H₂C═CH(CH₂)_(s) CO₂R⁷⁷ is present, R⁶⁷CH═CH₂ is also present.

Also described herein is a compound of the formula:

wherein:

L¹ is a neutral monodentate ligand which may be displaced by said olefin, and L² is a monoanionic monodentate ligand, or L¹ and L² taken together are a monoanionic bidentate ligand, provided that said monoanionic monodentate ligand or said monoanionic bidentate ligand may add to said olefin;

Ar¹, Ar², Ar⁴, Ar⁵, Ar¹⁰, Ar¹¹, Ar¹² and Ar¹³ are each independently aryl or substituted aryl;

R¹ and R² are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R¹ and R² taken together form a ring, and R³ is hydrogen, hydrocarbyl or substituted hydrocarbyl or R¹, R² and R³ taken together form a ring;

R¹⁰ and R¹⁵ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl;

R¹¹, R¹², R¹³, R¹⁴, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R⁵⁰, R⁵¹, R⁵², R⁵³ and R⁵⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group, and provided that any two of these groups vicinal to one another taken together may form a ring;

K is N or CR²⁷;

R²² is hydrocarbyl, substituted hydrocarbyl, —SR¹¹⁷, —OR¹¹⁷, or —NR¹¹⁸ ₂, R²⁴is hydrogen, a functional group, hydrocarbyl or substituted hydrocarbyl, and R²⁷ is hydrocarbyl or substituted hydrocarbyl, and provided that R²² and R²⁴ or R²⁴ and R²⁷ taken together may form a ring;

R¹¹⁷ is hydrocarbyl or substituted hydrocarbyl;

each R¹¹⁸ is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;

G and L are both N or G is CR⁵⁷ and L is CR⁵⁵;

R⁵⁵, R⁵⁶ and R⁵⁷ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or any two of R⁵⁵, R⁵⁶ and R⁵⁷ taken together form a ring;

R⁷⁸ is hydrocarbyl or substituted hydrocarbyl;

R⁷⁹, R⁸⁰, R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸ and R⁸⁹ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;

R⁹⁰, R⁹¹, R⁹² and R⁹³ are each independently hydrocarbyl or substituted hydrocarbyl;

R⁹⁴ and R⁹⁵ are each independently hydrocarbyl or substituted hydrocarbyl;

R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;

both of T are S (sulfur) or NH (amino);

each E is N (nitrogen) or CR¹⁰⁸ wherein R¹⁰⁸ is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;

R¹⁰⁰, R¹⁰¹, R¹⁰², R¹⁰³, R¹⁰⁴, R¹⁰⁵, R¹⁰⁶, and R¹⁰⁷ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;

R¹⁰⁹, R¹¹⁰, R¹¹¹, R¹¹², R¹¹³, R¹¹⁴, R¹¹⁵ and R¹¹⁶ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group; and

R²⁸ and R²⁹ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl.

Also disclosed herein is a compound of the formula

wherein:

R⁵⁸, R⁵⁹, R⁶⁰, R⁶², R⁶³ and R⁶⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group, and provided that any two of these groups vicinal to one another taken together may form a ring, or if vicinal to R⁶¹ or R⁶⁵ form a ring with them;

R⁶⁶ is hydrogen, hydrocarbyl or substituted hydrocarbyl; and

R⁶¹ and R⁶⁵ are each independently hydrocarbyl containing 2 or more carbon atoms, or substituted hydrocarbyl containing 2 or more carbon atoms, and provided that R⁶¹ and R⁶⁵ may form a ring with any group vicinal to it.

This invention also concerns a compound of the formula

wherein:

R⁶⁸ is hydrocarbyl, substituted hydrocarbyl, —SR¹¹⁷, —OR¹¹⁷, or —NR¹¹⁸ ₂, R⁷⁶ is hydrogen, a functional group, hydrocarbyl or substituted hydrocarbyl, and R⁷⁵ is hydrocarbyl or substituted hydrocarbyl, and provided that R⁶⁸ and R⁷⁶ or R⁷⁵ and R⁷⁶ taken together may form a ring;

R¹¹⁷ is hydrocarbyl or substituted hydrocarbyl;

each R¹¹⁸ is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;

R⁷⁰, R⁷¹ and R⁷² are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;

R⁶⁹ and R⁷³ are hydrocarbyl containing 3 or more carbon atoms, substituted hydrocarbyl containing 3 or more carbon atoms or a functional group;

and provided that any two of R⁷⁰, R⁷¹, R⁷², R⁶⁹ and R⁷³ vicinal to one another together may form a ring.

DETAILS OF THE INVENTION

Herein, certain terms are used. Some of them are:

A “hydrocarbyl group” is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is preferred that hydrocarbyl groups herein preferably contain 1 to about 30 carbon atoms.

By “substituted hydrocarbyl” herein is meant a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain preferably 1 to about 30 carbon atoms. Included in the meaning of “substituted” are heteroaromatic rings.

By “(inert) functional group” herein is meant a group other than hydrocarbyl or substituted hydrocarbyl which is inert under the process conditions to which the compound containing the group is subjected. The functional groups also do not substantially interfere with any process described herein that the compound in which they are present may take part in. Examples of functional groups include halo (fluoro, chloro, bromo and iodo), ether such as —OR²⁵, —CO²R²⁵, —NO₂, a —NR²⁵ ₂, wherein R²⁵ is hydrocarbyl or substituted hydrocarbyl. In cases in which the functional group may be near a nickel atom the functional group should not coordinate to the metal atom more strongly than the groups in compounds which are shown as coordinating to the metal atom, that is they should not displace the desired coordinating group.

By a “polymerization process” herein (and the polymers made therein) is meant a process which produces a polymer with a degree of polymerization (DP) of about 5 or more, preferably about 10 or more, more preferably about 40 or more [except where otherwise noted, as in P in compound (XVII)]. By “DP” is meant the average number of repeat (monomer) units in the polymer.

By “aryl” herein is meant a monovalent radical whose free valence is to a carbon atom of an aromatic ring. Unless otherwise noted herein, preferred aryl groups contain carbocyclic rings, but heterocyclic rings are also included within the definition of “aryl”. The aryl radical may contain one ring or may contain 2 or more fused rings, such as 9-anthracenyl or 1-naphthyl. Unless otherwise stated aryl groups preferably contain 5 to 30 carbon atoms.

By “substituted aryl” herein is meant an aryl radical substituted with one or more groups that do not interfere with the synthesis of the compound or the resulting polymerization. Suitable substituents include alkyl, aryl such as phenyl, halo, alkoxy, ester, dialkylamino and nitro. Unless otherwise stated, substituted aryl groups contain 5 to about 30 carbon atoms.

By a “monoanionic ligand” is meant a ligand with one negative charge.

By a “neutral ligand” is meant a ligand that is not charged.

“Alkyl group” and “substituted alkyl group” have their usual meaning (see above for substituted under substituted hydrocarbyl). Unless otherwise stated, alkyl groups and substituted alkyl groups preferably have 1 to about 30 carbon atoms.

By a styrene herein is meant a compound of the formula

wherein R⁴³, R⁴⁴, R⁴⁵, R⁴⁶ and R⁴⁷ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, all of which are inert in the polymerization process. It is preferred that all of R⁴³, R⁴⁴, R⁴⁵, R⁴⁶ and R⁴⁷ are hydrogen. Styrene (itself) is a preferred styrene.

By a norbornene is meant ethylidene norbornene, dicyclopentadiene, or a compound of the formula

wherein R⁴⁰ is hydrogen or hydrocarbyl containing 1 to 20 carbon atoms. It is preferred that R⁴⁰ is hydrogen or alkyl, more preferably hydrogen or n-alkyl, and especially preferably hydrogen. The norbornene may be substituted by one or more hydrocarbyl, substituted hydrocarbyl or functional groups in the R⁴⁰ or other positions, with the exception of the vinylic hydrogens, which remain. Norbornene (itself), dimethyl endo-norbornene-2,3-dicarboxylate, t-butyl 5-norbornene-2-carobxylate are preferred norbornenes and norbornene (itself) is especially preferred.

By a π-allyl group is meant a monoanionic ligand with 3 adjacent sp² carbon atoms bound to a metal center in an η³ fashion. The three sp2 carbon atoms may be substituted with other hydrocarbyl groups or functional groups. Typical π-allyl groups include

wherein R is hydrocarbyl. By a π-benzyl group is meant π-allyl ligand in which two of the sp² carbon atoms are part of an aromatic ring. Typical π-benzyl groups include

π-Benzyl compounds usually initiate polymerization of the olefins fairly readily even at room temperature, but π-allyl compounds may not necessarily do so. Initiation of 7E-allyl compounds can be improved by using one or more of the following methods:

Using a higher temperature such as about 80° C.

Decreasing the bulk of the monoanionic ligand, such as aryl being 2,6-dimethylphenyl instead of 2,6-diisopropylphenyl.

Making the π-allyl ligand more bulky, such as using

rather than the simple π-allyl group itself.

Having a Lewis acid or a material that acts as a Lewis acid present while using a π-allyl or π-benzyl group, especially a functional π-allyl or π-benzyl group. Relatively weak Lewis acids such as triphenylborane, tris(pentafluorophenyl)borane, tris(3,5-trifluoromethylphenyl)borane, and poly(methylaluminoxane) are preferred. Suitable functional groups include chloro and ester.

Lewis acids may also be optionally present when compounds containing L¹ and/or L² are present in the polymerization, even when L² is not a π-allyl or π-benzyl group. It is believed that the Lewis acid, if present, may help to remove L¹ (if present) from the nickel atom, thereby facilitating the coordination of the olefin to the Ni atom. If a compound containing L¹ and/or L² does not act as a polymerization catalyst, it is suggested that a Lewis acid, such as those mentioned above be added to the process to determine if polymerization will then take place. Such testing requires minimal experimentation, and is illustrated in the Examples. Not surprisingly, with any particular set of polymerization process ingredients, some Lewis acids may be more effective than others.

In preferred olefins herein, R⁶⁷ is hydrogen or α-alkyl containing 1 to 20 carbon atoms (an α-olefin), more preferably n-alkyl containing 1 to 8 carbon atoms, or more preferably hydrogen (e.g., ethylene) or methyl (e.g., propylene), and especially preferably hydrogen. A combination of ethylene and H₂C═CHR⁶⁷ wherein R⁶⁷ n-alkyl containing 1 to 8 carbon atoms is also preferred, and a combination of ethylene and propylene is more preferred. It is also preferred that s is 2 or more, and/or R⁷⁷ is alkyl, especially preferably methyl or ethyl. When H₂C═CH(CH₂)_(s)CO₂R⁷⁷ is present as one of the olefins, it is preferred that R⁶⁷ is hydrogen.

While not all homopolymers and copolymers of the olefinic monomers useful herein can be made using the polymerization processes described herein, most homopolymers and many copolymers can be made. The following homopolymers can be readily made in these polymerization processes: polyethylene, polystyrene, a polynorbornene, poly-α-olefins (often lower molecular weight polymers obtained), polycyclopentene (often lower molecular weight polymers obtained). Attempted homopolymerization of functionalized norbornenes often does not proceed, nor do homopolymerizations of compounds of the formula H₂C═CH(CH₂)_(s)CO₂R⁷⁷. Many copolymers can be made, including ethylene/α-olefins, styrene/norbornene copolymers, copolymers of 2 or more norbornenes including functionalized norbornenes, copolymers of ethylene and cyclopentene, copolymers of ethylene and a norbornene, and copolymers of ethylene and H₂C═CH(CH₂)_(s)CO₂R⁷⁷.

Not every variation of every nickel complex listed in the various polymerizations will make every one of the polymers listed immediately above. However, many of them will make most if not all of these types of polymers. While no hard and fast rules can be given, it is believed that for polymerizations which include ethylene and/or α-olefins, steric hindrance about the nickel atom caused by substituent groups is desirable for making polymers, especially higher molecular weight polymers, while for polymers containing one or more of a styrene and/or a norbornene such steric hindrance is not as important.

The Ni[II] complexes that are useful herein for the polymerization of ethylene contain a bidentate monoanionic ligand (other than a combined L¹ and L² ) in which the coordinating atoms are 2 nitrogen atoms, a nitrogen atom and an oxygen atom, a phosphorous atom and a sulfur atom, or an oxygen atom and a sulfur atom. Compounds of formulas (I) through (VI), (XVIII), (XXVII), and (XXXVII)-(XXXX) can be made by reaction of 2 moles of the anionic form of the ligand with one mole of the appropriate nickel allyl or benzyl precursor (XXI),

wherein X is preferably chlorine or bromine and A is a π-allyl or π-benzyl group, to form the nickel compound (see Examples 17-40 and 469-498).

Compounds of formulas (VII) through (XII), (XIX), (XXVIII), and (XXXXI)-(XXXXIV) can be synthesized by protonation of a suitable Ni[0] or Ni[II] precursor by the neutral ligand or by reaction of a suitable Ni[II] precursor with the anionic form of the ligand. Examples of suitable Ni[0] and Ni[II] precursors include Ni(1,4-cyclooctadiene)₂, (N,N,N′N′-tetramethylethylenediamine)NiMe₂, 2,2′-bipyridineNiMe₂, (MePPh₂)₃NiMe₂, [Ni(OMe)Me(PPh₃)]₂, [Ni(OMe)Me(PMe₃)]₂, NiBr₂, N,N,N′N′-tetramethylethylenediamine)Ni (acetylacetonate)₂, (1,2-dimethoxyethane)NiBr₂, N,N,N′N′-tetramethylethylenediamine)Ni(CH₂═CHCO₂CH₃)₂, (pyridine)₂Ni(CH₂═CHCO₂CH₃)₂, and (acetylacetonate)Ni(Et)(PPh₃). The addition of phosphine or ligand “sponges” such as CuCl, BPh₃ or tris(pentafluorophenyl)borane may aid such reactions.

Some of the nickel compounds herein such as (XXXIX), (XXXX), (XXXXIII) and (XXXXIV) may exist as “dimers” or monomers, or in equilibrium between the two. The dimer contains two nickel atoms, each nickel atom being coordinated to L¹ and L², wherein L¹ and L² combined may be a bidentate monoanionic ligand such as a π-allyl or π-benzyl group, and both Ni atoms “share” coordination to each of the other ligands present. As described herein, depiction of the monomeric compound also includes the dimeric compound, and vice versa. Whether any particular nickel compound is (predominantly) a monomer or dimer, or both states are detectable will depend on the ligands present. For instance it is believed that as the ligands become more bulky, especially about the nickel atom, the tendency is to form a monomeric compound.

Ligands for compounds (I) and (VII) of the formula

can be made by reaction of an alpha-diimine of the formula Ar¹N═CR¹—CR²═NAr² with one equivalent of a compound of the formula R³ Li, see for instance M. G. Gardner, et al., Inorg. Chem., vol. 34 p. 4206-4212 (1995). In another case, a ligand of the formula

can be made by the condensation of 1,2-cyclohexadione with the corresponding aromatic amine(s), see for instance R. van Asselt, et. al, Recl. Trav. Chim. Pays-Bas, vol. 113, p. 88-98 (1994). Note that in (XXIII) R¹, R² and R³ taken together form a ring, with R² and R³ both “part of” a double bond to the same carbon atom. These ligands can then be converted to their corresponding nickel complexes by the methods described above.

Compounds of the formula (II) can be made by the reaction of a ligand of the formula

while compounds of the formula (VIII) can be made from the protonated form of (XIII). (XIII) can be made from the corresponding salicylaldehyde (when R¹⁰ is hydrogen) and aromatic amine, followed by reaction with an alkali metal base (such as an alkali metal hydride) to form the aryloxide.

(III) and (IX) can be made by reacting pyrrole-2-carboxyaldehyde with the appropriate aromatic amine to form the pyrrole-2-imine, followed by reaction with a strong base to form the pyrrole anion, and then reaction with the nickel precursors described above to form the nickel[II] complex.

Similarly, (IV) and (X) can be formed from an alkali metal thiophene-2-carboxylate and the nickel precursors described above.

When K is CR²⁷ the ligand for (V) and (XI) can be made by the reaction of the corresponding ketone (which may contain other functional groups) with an aromatic amine to give

which is a tautomer of

Useful ketones for making (V) and (XI) include ethyl acetoacetate, ethyl 2-ethylacetoacetate, isobutyl acetoacetate, t-butyl acetoacetate, S-t-butyl acetoacetate, allyl acetoacetate, ethyl 2-methylacetoacetate, methyl 2-chloroacetoacetate, ethyl 2-chloroacetoacetate, methyl 4-chloroacetoacetate, ethyl 4-chloroacetoacetate, ethyl 4,4,4-trifluoroacetoacetate, S-methyl 4,4,4-trifluoro-3-oxothiobutyrate, 2-methoxyethyl acetoacetate, methyl 4-methoxyacetoacetate, methyl propionylacetate, ethyl propionyl acetate, ethyl isobutyrylacetate, methyl 4,4-dimethyl-3-oxopentanoate, ethyl bytyrylacetate, ethyl 2,4-dioxovalerate, methyl 3-oxo-6-octenoate, dimethyl 1,3-acetonedicarboxylate, diethyl 1,3-acetonedicarboxylate, di-t-butyl 1,3-acetonedicarboxylate, dimethyl 3-oxoadipate, diethyl 3-oxopimelate, dimethyl acetylsuccinate, diethyl acetylsuccinate, diethyl 2-acetylglutarate, methyl 2-cyclopentatecarboxylate, ethyl 2-cyclopentanecarboxylate, ethyl 4-methyl-2-cyclohexanone-1-carboxylate, ethyl 4-methyl-2-cyclohexanone-1-carboxylate, ethyl 3-(1-adamantyl)-3-oxopropionate, methyl 2-oxo-1-cycloheptanecarboxylate, N-t-butylacetoamide, 2-chloro-N,N-dimethylacetoacetamide, 4,4,4-trifluoro-1-phenyl-1,3-butanedione, 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione, 2-acetyl-1-tetralone, ethyl 2-benzylacetoacetonate, methyl 1-benzyl-4-oxo-3-piperidinecarboxylate hydrochloride, benzyl acetoacetate, acetoacetanilide, o-acetoacetotoluide, N-(2,4-dimethylphenyl)-3-oxobutyramide, o-acetoacetanisidide, 41-chloroacetoacetanilide, and 1,1,1-trifluoro-3-thianoylacetone.

When K is N in (V) and (XI), and R²⁴ is nitrile, the ligand can made by the reaction of R²²C(O)CH₂CN with the diazonium salt of the corresponding arylamine, see for instance V. P. Kurbatov, et al., Russian Journal of Inorganic Chemistry, vol. 42, p. 898-902(1997). This paper also reviews methods of making ligands wherein K is CR²⁷.

The boron containing ligands needed for compounds (VI) and (XII),

can be made by known procedures, see for instance S. Trofimenko, Prog. Inorg. Chem., vol. 34, p. 115-210 (1986) and S. Trofimenko, Chem. Rev., vol. 93, p. 943-980 (1993).

The synthesis of the tropolone-type ligands required for (XVIII) and (XIX) are described in J. J. Drysdale, et al., J. Am. Chem. Soc., vol. 80, p. 3672-3675 (1958); W. R. Brasen, et al., vol. 83, p. 3125-3138 (1961); and G. M. Villacorta, et al., J. Am. Chem. Soc., vol. 110, p. 3175-3182 (1988). These can be reacted as described above to form the corresponding nickel complex.

The ligand for (XXVII) and (XXVIII),

or either of its tautomers,

can be made by reaction of the appropriate α,χ-dioxo compound such as a 1,3-dione or 1,3-dial or similar compound with the appropriate aromatic amine, see for instance J. E. Parks, et al., Inorg. Chem., vol. 7, p. 1408 (1968); R. H. Holm, Prog. Inorg. Chem., vol. 14, p. 241 (1971); and P. C. Healy, et al., Aust. J. Chem., vol. 32, p. 727 (1979).

If the ligand precursor may form a tautomer, the ligand itself may usually be considered a tautomer. For instance, the monoanionic ligand derived from (XXIX) and it tautomers may be written as

In (XXVII) and (XXVIII) when L and/or G is N, the ligand can be made by the method described in Y. A. Ibrahim, et al., Tetrahedron, vol. 50, p. 11489-11498(1994) and references described therein.

The ligands for (XXXVII) and (XXXXI) can be made by methods described in Phosphorous, Sulfur and Silicon, vol. 47, p. 401 et seq. (1990), and analogous reactions.

The ligands for (XXXVIII) and (XXXXII) can be made by reacting R₂PLi (from R₂PH and n-BuLi) with propylene sulfide to form R₂CH₂CH(CH₃)SLi, and analogous reactions.

The ligands for (XXXIX) and (XXXXIII), and for (XXXX) and (XXXXIV) are commercially available. Those used herein were bought from Aldrich Chemical Co., Inc., Milwaukee, Wis., U.S.A.

In the compounds (and ligands in those compounds) (I) through (XII), (XVIII), (XIX), (XXVII), (XXVIII), and (XXXVII)-(XXXXIV), certain groups are preferred. When present, they are:

R¹ and R² are both hydrogen; and/or

R³ is alkyl or aryl containing 1 to 20 carbon atoms, more preferably R³ is t-butyl; and/or

R¹, R² and R³ taken together are

Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar¹⁰ and Ar¹¹ are each independently

wherein R³⁶, R³⁷, R³⁸, R³⁹ and R⁴⁰ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any 2 of R³⁷, R³⁷, R³⁸, R³⁹ and R⁴⁰ that are vicinal to one another taken together may form a ring (for example the group 9-anthracenyl), and it is especially preferred that R³⁶ and R³⁹ are halo, phenyl or alkyl containing 1 to 6 carbon atoms, and it is more preferred that R³⁶ and R³ are methyl, bromo, chloro, t-butyl, hydrogen, or isopropyl; and/or

R⁷⁸ is Ar³, which is aryl or substituted aryl;

Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar¹⁰ and Ar¹¹ are each independently 2-pyridyl or substituted 2-pyridyl;

if a π-allyl group is

then R₄, R₅, R₆, and R₈ are hydrogen; and/or

R⁴, R⁵, R⁶, R₇, R⁸ and R⁹ are hydrogen; and/or

R⁴, R⁵, R⁶, and R⁷ are hydrogen and R⁸ and R⁹ are methyl;

one of R⁷ or R⁹ is —CO₂R⁴¹ or chloro, and the other is hydrogen, and wherein R⁴¹ is hydrocarbyl, preferably alkyl containing 1 to 6 carbon atoms; and/or

R¹¹, R¹², R¹³ and R¹⁴ are each independently chloro, bromo, iodo, alkyl, alkoxy, hydrogen or nitro; and/or

R¹¹ and R¹² taken together form an aromatic carbocyclic 6-membered ring; and/or

R¹⁴ and R¹² are both chloro, bromo, iodo, t-butyl or nitro; and/or

R¹¹ and R¹³ are methoxy;

R¹⁴ is hydrogen and R¹² is nitro; and/or

one or more of R¹¹, R¹², R¹³ and R¹⁴ are hydrogen; and/or

R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ are hydrogen; and/or

R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰ are hydrogen and R²¹ is methyl; and/or

K is CR²⁷; and/or

R²⁷ is hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group; and/or

R²⁷ is alkyl, more preferably methyl; and/or

R²⁴ is hydrogen, alkyl, cyano, or halo, more preferably hydrogen; and/or

R²² is hydrocarbyl or —OR¹¹⁷, wherein R¹¹⁷ is hydrocarbyl, more preferably alkyl containing 1 to 6 carbon atoms, or R²² is phenyl; and/or

R³² and R³³ are both alkyl containing 1 to 6 carbon atoms or phenyl, more preferably isopropyl; and/or

R²⁸ and R²⁹ are both hydrogen or phenyl; and/or

R³⁰, R³¹, R³⁴ and R³⁵ are all hydrogen; and/or

R³¹ and R³² taken together and R³³ and R³⁴ taken together are both a 6-membered aromatic carbocyclic ring having a t-butyl group vicinal to the R³² and R³³ positions; and/or

R⁵⁰, R⁵¹, R⁵², R⁵³ and R⁵⁴ are hydrogen; and/or

L is CR⁵⁵ wherein R⁵⁵ is hydrocarbyl, hydrogen, or substituted hydrocarbyl; and/or

G is CR⁵⁷ wherein R⁵⁷ is hydrocarbyl, hydrogen or substituted hydrocarbyl; and/or

more preferably R⁵⁵ and R⁵⁷ are both alkyl or fluorinated alkyl, more preferably methyl; and/or

R⁵⁶ is hydrogen; and/or

Ar¹² and Ar₁₃ are both 2,6-diisopropylphenyl; and/or

R⁷⁹, R⁸⁰, R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸ and R⁸⁹ are each independently hydrogen or alkyl; and/or

R₉₀, R₉₁, R₉₂ and R₉₃ are each independently hydrocarbyl, more preferably aryl, and especially referably phenyl; and/or

R⁹⁴ and R⁹⁵ are each independently hydrocarbyl; and/or

R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹ are each independently hydrogen or hydrocarbyl; and/or

E is N or CR¹⁰⁸; and/or

R¹⁰⁸ is hydrogen or hydrocarbyl; and/or

R¹⁰⁰, R¹⁰¹, R¹⁰², R¹⁰³, R¹⁰⁴, R¹⁰⁵, R¹⁰⁶, and R¹⁰⁷ is each independently hydrogen, hydrocarbyl, or halo; and/or

R¹⁰⁹, R¹¹⁰, R¹¹¹, R¹¹², R¹¹³, R¹¹⁴, R¹¹⁵, and R¹¹⁶ are each independently hydrogen or hydrocarbyl.

Specific preferred compounds (I)-(IV) and (VI) are given in Table A. The same groupings shown in the Table are preferred for the analogous compounds (VII)-(X) and (XII). In all of these compounds, where applicable, R⁴, R⁵, R⁶, R⁸, R⁹ [in (XX) above], R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R³⁰, and R³⁵ are all hydrogen (with the exceptions in the footnotes), R¹⁰ is hydrogen or methyl, R²¹ is hydrogen or methyl, and R⁷ is —CO₂CH₃ (with the exceptions in the footnotes). In compounds wherein L₁ and L₂ appear, and especially in compounds of formula (VIII) it is preferred that L₂ is a nitrile, such as benzonitrile, p-methylbenzonitrile methyl nitrile, or pyridine or a substituted pyridine such as 2,6-dimethyl pyridine. A preferred L₂ is an alkyl group, especially methyl. L₁ and L₂ taken together may be a π-allyl or π-benzyl group, but for all compounds in which L₁ and L₂ are present (i.e. combined) it is preferred that they are not a π-allyl or π-benzyl group.

Table B give specific preferred compounds for (V), (XXXVII) and (XXXIX) as well as the corresponding compounds (XI), (XXXXI) and (XXXXIII) respectively. In all of these compounds Ar⁵ is 2,6-diisopropylphenyl, K is CCH₃, R²⁴, R⁷⁹, R⁸⁰, R⁸², R⁸⁵, R⁸⁷, R⁸⁸, and R⁸⁹ are hydrogen, R⁹⁰, R⁹¹, R⁹², and R⁹³ are phenyl.

In a specific preferred compounds (XXVII) and the corresponding (XXVIII), Ar¹² and Ar¹³ are 2,6-diisopropylphenyl, L and G are CCH₃, and R⁵⁶ is hydrogen.

In a specific preferred compound (XXXVIII) and the corresponding (XXXXVII), R⁹⁴ and R⁹⁵ are each cyclohexyl, R⁹⁶, R⁹⁷ and R⁹⁸ are hydrogen, and R⁹⁹ is methyl.

In a specific preferred compound (XXXX) and the corresponding (XXXXIV), R¹¹⁰, R¹¹¹, R¹¹⁴ and R¹¹⁵ are hydrogen and R¹⁰⁹, R¹¹², R¹¹³ and R¹¹⁶ are methyl.

TABLE A Cmpd^(c) R¹ R² R³ Ar¹ and Ar² Ar³ R¹¹ R¹² R¹³ R¹⁴ Ar⁴ Ia ^(a) ^(a) ^(a) 2,6-i-Pr—Ph — — — — — — Ib H H t-butyl 2,6-i-Pr—Ph — — — — — — IIa — — — — 2,6-i-Pr—Ph H t-butyl H t-butyl — IIb — — — — 2,6-i-Pr—Ph ^(b) ^(b) H H — IIc — — — — 2,6-Me—Ph ^(b) ^(b) H H — IId — — — — 2,6-Me—Ph H Cl H Cl — IIe — — — — 2,6-i-Pr—Ph H Cl H Cl — IIf — — — — 2,6-i-Pr—Ph H NO₂ H NO₂ — IIg — — — — 2,4,6-t-butyl-Ph H NO₂ H NO₂ — IIh — — — — 2,6-Br-4-Me—Ph H NO₂ H NO₂ — IIi — — — — 2,6-Me—Ph H NO₂ H NO₂ — IIj — — — — 2,6-i-Pr—Ph H NO₂ H H IIk — — — — 2-t-Bu—Ph H NO₂ H NO₂ IIl — — — — 2,6-Me—Ph H t-butyl H t-butyl IIm — — — — 2,6-Br-4-F—Ph H t-butyl H t-butyl IIn — — — — 2-Cl-6-Me—Ph H NO₂ H NO₂ IIo — — — — ^(f) H NO₂ H NO₂ IIp — — — — 2,6-i-Pr—Ph H I H I IIq — — — — 2,6-i-Pr—Ph OMe H OMe H IIr — — — — 2,6-Br-4-F—Ph ^(b) ^(b) H H IIs — — — — 3-Me-1-pyridyl ^(b) ^(b) H H IIt — — — — 2-t-Bu—Ph ^(b) ^(b) H H IIu — — — — ^(e) H H H H IIIa — — — — — — — — — 2,6-i-Pr—Ph VIa — — — — — — — — — — VIb — — — — — — — — — — Cmpd^(c) R²⁸ R²⁹ R³⁰ R³¹ R³² R³³ R³⁴ R³⁵ Ia — — — — — — — — Ib — — — — — — — — IIa — — — — — — — — IIb — — — — — — — — IIc — — — — — — — — IId — — — — — — — — IIe — — — — — — — — IIf — — — — — — — — IIg — — — — — — — — IIh — — — — — — — — IIi — — — — — — — — IIj IIk IIl IIm IIn IIo IIp IIq IIr IIs IIt IIu IIIa — — — — — — — — VIa H H H ^(d) ^(d) ^(d) ^(d) H VIb Ph Ph H H i-propyl i-propyl H H ^(a)R¹, R² and R³ taken together are ═CH—CH₂—CH₂—CH₂— wherein a vinylic carbon is vicinal to the amino nitrogen atom. ^(b)R¹¹ and R¹² taken together form a 6 membered aromatic ring (the two fused rings together form a naphthalene group). ^(c)R⁷ in (XX) is —CO₂CH₃. All other groups in (XX) are H. ^(d)R³¹ and R³², and R³³ and R³⁴, each pair taken together form a 6-membered aromatic carbocyclic ring substituted with a t-butyl group at the carbon atoms vicinal to the R³² and R³³ positions. ^(e)R¹⁰ and R⁷⁸ taken together are, respectively, —OCH₂C(CH₃)₂— wherein the oxygen atom is attached to a carbon atom. ^(f)1,2,3,4-tetrahydro-1-naphthyl

TABLE B Cmpd R²² R⁸¹ R⁸³ R⁸⁴ R⁸⁶ T E R¹⁰⁰ R¹⁰¹ R¹⁰² R¹⁰³ R¹⁰⁴ R¹⁰⁵ R¹⁰⁶ R¹⁰⁷ Va OMe — — — — — — — — — — — — — — Vb Me — — — — — — — — — — — — — — XXXVIIa — Me H H Me — — — — — — — — — — XXXVIIb — H Me Me H — — — — — — — — — — XXXIXa — — — — — S N Cl Cl Cl Cl Cl Cl Cl Cl XXXIXb — — — — — NH CCH₃ Br H H Br Br H H Br

For clarity, the structures of compounds (Ia), (IIb) and (VIa) are shown below;

In (XXXIII) it is preferred that:

R⁵⁸, R⁵⁹, R⁶⁰, R⁶², R⁶³ and R⁶⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group, and provided that any two of these groups vicinal to one another taken together may form a ring;

R⁶⁶ is hydrogen, hydrocarbyl or substituted hydrocarbyl; and

R⁶¹ and R⁶⁵ are each independently hydrocarbyl containing 2 or more carbon atoms, or substituted hydrocarbyl containing 2 or more carbon atoms.

R⁵⁸, R⁵⁹, R⁶⁰, R⁶², R⁶³ and R⁶⁴ are each hydrogen; and/or

R⁶⁶ is hydrogen; and/or

R⁶¹ and R⁶⁵ are each independently alkyl, and more preferred that both are isopropyl or methyl.

In a preferred compound or ligand (XVIII) and (XIX):

R⁵⁰, R⁵¹, R⁵², R⁵³ and R⁵⁴ are hydrogen; and/or

Ar¹⁰ and Ar¹¹ are 2,6-dialkyl substituted phenyl, more preferably 2,6-dimethylphenyl or 2,6-diisopropylphenyl.

Monoanionic ligands which the olefins herein may add to include hydride, alkyl, substituted alkyl, aryl, substituted aryl, or R²⁶C(═O)— wherein R²⁶ is hydrocarbyl or substituted hydrocarbyl, and groups π-allyl and π-benzyl groups such as η³-C₈H₁₃, see for instance J. P. Collman, et al., Principles and Applications of Organotransition Metal Chemistry, University Science Book, Mill Valley, Calif., 1987. Such groups are also described in World Patent Application WO 96/23010.

In compound (XXXVI) it is preferred that R⁶⁸ is —OR¹¹⁷ or aryl, and/or R⁷⁵ is hydrocarbyl or substituted hydrocarbyl, and/or R⁷⁶ is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, more preferably hydrogen, hydrocarbyl or substituted hydrocarbyl.

In the second polymerization process described herein a nickel[II] complex such as any one of (VII)-(XII), (XIX), (XXVIII) or (XXXXI)-(XXXXIV) is either added to the polymerization process or formed in situ in the process. In fact, more than one such complex may be formed during the course of the process, for instance formation of an initial complex and then reaction of that complex to form a living ended polymer containing such a complex.

An example of such a complex which may be formed initially in situ is

wherein R¹ through R³, Ar¹ and Ar² are as defined above, T¹ is hydride, alkyl, or R⁴²C(═O)— wherein R⁴² is hydrocarbyl or substituted hydrocarbyl or any other monoanionic ligand which ethylene may add to, and Y is a neutral ligand, or T¹ and Y taken together are a bidentate monoanionic ligand which ethylene may add to. Similar complexes may also be formed with the ligands in (VIII)-(XII), (XIX), (XXVIII) and (XXXXI)-(XXXXIV). Such complexes may be added directly to the process or formed in situ.

After the olefin polymerization has started, the complex may be in forms such as

wherein R¹ through R³ ₁, Ar¹ and Ar² are as defined above, P is a divalent (poly)olefin group [the specific olefin shown in (XVI) and (XVII) is ethylene], —(CH2)_(x)— wherein x is an integer of 2 or more, and T¹ is an end group, for example the groups listed for T¹ above. (XVI) is a so-called agostic form complex. Similar complexes may also be formed with the ligands in (VIII)-(XII), (XI), (XXVIII) and (XXXXI)-(XXXXIV). Analogous compounds with other olefins in place of ethylene also may be formed. In all the polymerization processes herein, the temperature at which the olefin polymerization is carried out is about −100° C. to about +200° C., preferably about 0° C. to about 150° C., more preferably about 25° C. to about 100° C. The olefin concentration at which the polymerization is carried out is not critical, atmospheric pressure to about 275 MPa being a suitable range for ethylene and propylene.

The polymerization processes herein may be run in the presence of various liquids, particularly aprotic organic liquids. The catalyst system, olefin, and polyolefin may be soluble or insoluble in these liquids, but obviously these liquids should not prevent the polymerization from occurring. Suitable liquids include alkanes, cycloalkanes, selected halogenated hydrocarbons, and aromatic hydrocarbons. Hydrocarbons are the preferred solvent. Specific useful solvents include hexane, toluene, benzene, chloroform, methylene chloride, 1,2,4-trichorobenzene, p-xylene, and cyclohexane.

The catalysts herein may be “heterogenized” by coating or otherwise attaching them to solid supports, such as silica or alumina. Where an active catalyst species is formed by reaction with a compound such as an alkylaluminum compound, a support on which the alkylaluminum compound is first coated or otherwise attached is contacted with the nickel compound precursor to form a catalyst system in which the active nickel catalyst is “attached” to the solid support. These supported catalysts may be used in polymerizations in organic liquids, as described in the immediately preceding paragraph. They may also be used in so-called gas phase polymerizations in which the olefin(s) being polymerized are added to the polymerization as gases and no liquid supporting phase is present.

Included herein within the definitions of all the polymerization processes are mixtures of starting materials that lead to the formation in situ of the nickel compounds specified in all of the polymerization processes.

In the Examples all pressures are gauge pressures.

Quantitative 3C NMR data for the polymers was obtained using a 10 mm probe on typically 15-20% solutions of the polymer and 0.05M Cr(acetylacetonate)₃ in 1,2,4-trichlorobenzene are 120-140° C. For a full description of determination of branching by ¹³C and ¹H NMR, and for a definition of branches, see World Patent Application 96/23010, which is hereby included by reference.

In the Examples, the following abbreviations are used:

Am—amyl

Bu—butyl

Cy—cyclohexyl

E—ethylene

Et—ethyl

GPC—gel permeation chromatography

Me—methyl

MI—melt index

Mn—number average molecular weight

Mw—weight average molecular weight

MW—molecular weight

N—norbornene

P—propylene

PE—polyethylene

PDI—polydispersity, Mw/Mn

PMAO—poly(methylaluminoxane)

Pr—propyl

RI—refractive index

rt—room temperature

S—styrene

TCB—1,3,5-trichlorobenzene

THF—tetrahydrofuran

Tm—melting point

tmeda—N,N,N′,N′-tetramethylethylenediamine

TO—turnovers, moles of monomer polymerized per mole of catalyst (nickel compound) used

EXAMPLES 1-16 Ligand Syntheses

Ligand syntheses and deprotonations were carried out according to the general procedures given below unless stated otherwise. The general procedure for imine synthesis is based upon published procedures for the synthesis of N-aryl-substituted imines given in the following reference: Tom Dieck, H.; Svoboda, M.; Grieser, T. Z. Naturforsch 1981, 36b, 823-832. The synthesis of ArN═CH—CH(t-Bu)—N(Ar)(Li) [Ar=2,6-(i-Pr)₂C₆H₃] is based on the published synthesis of (t-Bu)N═CH—CH(t-Bu)—N(t-Bu)(Li): Gardiner, M. G.; Raston, C. L. Inorg. Chem. 1995, 34, 4206-4212. The synthesis of ArN═C(Me)—CH═C(Me)—NH(Ar) [Ar=2,6-(i-Pr)₂C₆H₃] was published in WO Pat. Appl. 96/23010, and it was deprotonated according to the general procedure given below. The bis(pyrazolyl)borate anions that were used to synthesize complexes 18 and 19 were provided by S. Trofimenko (DuPont) and were synthesized according to the procedures published in the following review: Trofimenko, S. Chem. Rev. 1993, 93, 943.

General Procedure for Imine Synthesis. In a fume hood, formic acid catalyst was added to a methanol solution of the aldehyde and the aniline (˜1.1-1.2 equiv). The reaction mixture was stirred and the resulting precipitate was collected on a frit and washed with methanol. The product was then dissolved in Et₂O or CH₂Cl₂ and stirred over Na₂SO₄ overnight. The solution was filtered through a frit with Celite® and the solvent was removed in vacuo to yield the product.

General Procedure for the Synthesis of Sodium Salts. The protonated forms of the ligands were dissolved in anhydrous THF in the drybox. Solid NaH was slowly added to the solution, and then the reaction mixture was stirred overnight. The next day, the solution was filtered through a frit with dry Celite®. The solvent was removed and the resulting powder was dried in vacuo. With some exceptions (e.g., Example 1), the sodium salts were not soluble in pentane and were further purified by a pentane wash.

EXAMPLE 1

A drop of formic acid was added to a solution of 1,2-cyclohexanedione (0.25 g, 2.2 mmol) and 2,6-diisopropylaniline (0.85 mL, 4.5 mmol) in 5 mL of methanol. The reaction mixture was stirred at rt for 3 days. The white solid thus formed was filtered, washed with a small amount of methanol and dried under vacuum. After recrystallization from hot methanol, the product (0.4 g; 41% yield; mp 81-83° C.) was isolated as white crystals: ¹H NMR (CDCl₃, 300 MHz, rt): δ 7.28-7.08 (m, 6, H_(aryl)), 6.45 (s, 1, NH), 4.84 (t, 1, J=4.6, —CH═CNHAr), 3.30 (septet, 2, J=6.88, CHMe₂), 2.86 (septet, 2, J=6.87, C′HMe₂), 2.22 (m, 4, ArN═CCH₂CH₂—), 1.75 (m, 2, CH₂CH═CNHAr), 1.24 and 1.22 (d, 12 each, CHMe₂ and C′HMe₂); ¹³C NMR (CDCl₃, 300 MHz, rt) δ 162.1, 147.3, 145.8, 139.6, 137.0, and 136.4 (ArNH—C—C═NAr, Ar: C_(ipso), C_(o); Ar′: C_(ipso), C_(o)), 126.5, 123.4, 123.3 and 122.9 (Ar: C_(p), C_(m); Ar′: C_(p), C_(m)), 106.0 (ArNHC═CH—), 29.3, 28.4 and 28.3 (ArNHC═CH—CH₂CH₂CH₂C═NAr), 24.2 and 23.30 (CHMe₂, C′HMe₂), 23.25 and 22.9 (CHMe₂, C′HMe₂).

The sodium salt was cleanly synthesized according to the above general procedure: ¹H NMR (300 MHz, THF-d₈): no THF coordinated.

EXAMPLE 2 ArN═CH—CH(t-Bu)—N(Ar)(Li) [Ar=2,6-(i-Pr)₂C₆H₃]

In a nitrogen-filled drybox, t-BuLi (7.81mL of a 1.7 M solution in pentane) was filtered through a short plug of dry Celite® into a round bottom flask. The flask was cooled to −35° C. in the drybox freezer. The diimine ArN═CH—CH═NAr [Ar=2,6-(i-Pr₂)C₆H₃] was added as a solid over a period of 15 min to the cold t-BuLi solution. The reaction mixture was stirred for ˜2 h to give a viscous red solution. The solution was diluted with pentane and then filtered through a frit with Celite®. The resulting clear solution was concentrated under vacuum and then cooled in the drybox freezer to −35 ° C. An orange powder was obtained (3.03 g, 51.8%, 1st crop): ¹H NMR (THF-d₈, 300 MHz, rt) δ 8.29 (s, 1, CH═N), 7.08 (d, 2, J=7.4, Ar: H_(m)), 7.00 (t, 1, J=7.0, Ar: H_(p)), 6.62 (m, 2, Ar: H_(m)), 6.14 (t, 1, J=7.4, Ar: H_(p)), 4.45 (s, 1, CH(t-Bu)), 3.08 (br septet, 2, CHMe₂), 3.05 (septet, 2, J=6.8, CHMe₂), 1.35 (d, 3, J=6.7, CHMe₂), 1.13 (d, 3, J=7.0, CHMe₂), 1.13 (br s, 12, CHMe₂), 1.02 (d, 3, J=6.7, CHMe₂), 0.93 (s, 9, CMe₃); ¹³C NMR (THF-d₈, 75 MHz, rt) δ 184.5 (N═CH), 161.9 and 150.1 (Ar, Ar′: C_(ipso)), 139.7, 139.5 (br), 139.0 (br) and 137.3 (Ar, Ar′: C_(o)), 125.0, 124.0, 123.5, 122.4 and 112.2 (Ar, Ar′: C_(m) and C_(p)), 80.8 (CH(t-Bu)), 41.5 (CMe₃), 29.3, 28.6, 27.8 (br), 26.5 (br), 26.3, 25.9, 25.6, 25.0 and 23.3 (br) (Ar, Ar′: CHMe₂; CMe₃)

EXAMPLE 3 [2-(OH)-3,5-(t-Bu)₂C₆H₂]—CH═NAr [Ar=2,6-(i-Pr)₂C₆H₃]

The general procedure for imine synthesis was followed using 10.1 g (43.0 mmol) of 3,5-di-t-butyl-2-hydroxybenzaldehyde and 9.91 g (55.9 mmol, 1.30 equiv) of 2,6-diisopropylaniline. A light yellow powder (10.5 g, 62.1%) was isolated: ¹H NMR (CDCl₃, 300 MHz, rt) δ 13.50 (s, 1, OH), 8.35 (s, 1, CH═NAr), 7.56 (d, 1, J=2.7, H_(aryl)), 7.22 (m, 4, H_(aryl)), 3.08 (septet, 2, J=6.8, CHMe₂), 1.55 (s, 9, CMe₃), 1.39 (s, 9, C′Me₃), 1.23 (d, 12, J=6.7, CHMe₂).

The sodium salt was cleanly synthesized according to the above general procedure: H NMR (300 MHz, THF-d₈): 0.63 equiv of THF coordinated.

EXAMPLE 4 [2-(OH)-3,5-(t-Bu)₂C₆H₂]—CH═NAr [Ar=2,6-Me₂C₆H₃]

The general procedure for imine synthesis was followed using 3.05 g (13.0 mmol) of 3,5-di-t-butyl-2-hydroxybenzaldehyde and 1.89 g (15.6 mmol, 1.20 equiv) of 2,6-dimethylaniline. A yellow powder (2.00 g, 45.6%) was isolated: ¹H NMR (CDCl₃, 300 MHz, rt, OH resonance not assigned) δ 8.34 (s, 1, CH═NAr), 7.50 and 7.16 (d, 1 each, H_(aryl)), 7.10 (d, 2, Ar: H_(m)), 7.01 (t, 1, Ar: H_(p)), 2.22 (s, 6, Ar: Me), 1.49 (s, 9, CMe₃), 1.34 (s, 9, C′Me₃).

The sodium salt was cleanly synthesized according to the above general procedure: H NMR (300 MHz, THF-d₈): 0.51 equiv of THF coordinated.

EXAMPLE 5 [2-(OH)-3,5-(t-Bu)₂C₆H₂]—CH═NAr [Ar=2,6-Br₂-4-F—C₆H₂]

The general procedure for imine synthesis was followed using 2.12 g (9.05 mmol) of 3,5-di-t-butyl-2-hydroxybenzaldehyde and 1.89 g (10.8 mmol, 1.20 equiv) of 2,6-dibromo-4-fluoroaniline. A yellow powder (1.11 g, 25.5%) was isolated: ¹H NMR (CDCl₃, 300 MHz, rt, OH resonance not assigned) δ 8.45 (s, 1, CH═NAr), 7.54 (d, 1, H_(aryl)), 7.40 (d, 2, J_(HF) ˜9, Ar: H_(m)), 7.19 (d, 1, H_(aryl)), 1.50 (s, 9, CMe₃), 1.35 (s, 9, C′Me₃).

The sodium salt was cleanly synthesized according to the above general procedure: 1H NMR (300 MHz, THF-d₈): 0.58 equiv of THF coordinated.

EXAMPLE 6 [2-(OH)-3,5-(NO₂)₂C₆H₂]—CH═NAr [Ar=2,6-(i-Pr)₂C₆H₃]

The general procedure for imine synthesis was followed using 4.98 g (23.5 mmol) of 3,5-dinitro-2-hydroxybenzaldehyde and 4.16 g (23.5 mmol) of 2,6-diisopropylaniline. A yellow powder (6.38 g, 73.1%) was isolated: ¹H NMR (CDCl₃, 300 MHz, rt, OH resonance not assigned) δ 9.06 (d, 1, H_(aryl)), 8.52 (d, 1, H_(aryl)), 8.31 (d, 1, J˜6, CH═NAr), 7.40 (t, 1, Ar: H_(p)), 7.30 (d, 2, Ar: H_(m)), 2.96 (septet, 2, CHMe₂), 1.25 (d, 12, CHMe₂).

The sodium salt was cleanly synthesized according to the above general procedure: ¹H NMR (300 MHz, THF-d₈): 0.57 equiv of THF coordinated.

EXAMPLE 7 [2-(OH)-3,5-(NO₂)₂C₆H₂]—CH═NAr [Ar=2,4,6-(t-Bu)₃C₆H₂]

The general procedure for imine synthesis was followed using 3.00 g (14.1 mmol) of 3,5-dinitro-2-hydroxybenzaldehyde and 3.88 g (14.9 mmol, 1.06 equiv) of 2,4,6-tris(t-butyl)aniline. A yellow powder (4.78 g, 74.5%) was isolated: ¹H NMR (CDCl₃, 300 MHz, rt, OH resonance not assigned) δ 9.09 (d, 1, H_(aryl)), 8.41 (d, 1, H_(aryl)), 8.16 (d, 1, J˜12, CH═NAr), 7.48 (s, 1, Ar: H_(m)), 1.38 (s, 18, CMe₃), 1.36 (s, 9 C′Me₃).

The sodium salt was cleanly synthesized according to the above general procedure: ¹H NMR (300 MHz, THF-d₈): 2 equiv of THF coordinated.

EXAMPLE 8 [2-(OH)-3,5-(NO₂)₂C₆H₂]—CH═NAr [Ar 2,6-Me₂C₆H₃]

The general procedure for imine synthesis was followed using 3.11 g (14.7 mmol) of 3,5-dinitro-2-hydroxybenzaldehyde and 1.96 g (16.1 mmol, 1.10 equiv) of 2,6-dimethylaniline. A yellow powder (3.63 g, 78.4%) was isolated: ¹H NMR (CDCl₃, 300 MHz, rt, OH resonance not assigned) δ 9.05 (d, 1, H_(aryl)), 8.52 (d, 1, H_(aryl)), 8.42 (d, 1, J˜9, CH═NAr), 7.22 (m, 3, Ar: H_(p) and H_(m)), 2.36 (s, 6, Ar: Me).

The sodium salt was cleanly synthesized according to the above general procedure: ¹H NMR (300 MHz, THF-d₈): 0.25 equiv of THF coordinated.

EXAMPLE 9 [2-(OH)-3,5-(NO₂)₂C₆H₂]—CH═NAr [Ar=2,6-Br₂₋₄-Me-C₆H₂]

The general procedure for imine synthesis was followed using 3.10 g (14.6 mmol) of 3,5-dinitro-2-hydroxybenzaldehyde and 4.64 g (17.5 mmol, 1.20 equiv) of 2,6-dibromo-4-methylaniline. A yellow powder (5.15 g, ˜76.8%) was isolated. The ¹H NMR spectrum of the product showed the presence of methanol, so the powder was dissolved in THF in the drybox under a nitrogen atmosphere and the solution was placed over molecular sieves for several days. The solution was then filtered through a frit with Celite® and the solvent was removed in vacuo: ¹H NMR (CDCl₃, 300 MHz, rt; OH resonance not assigned; ˜1 equiv of THF is present) δ 8.95 (d, 1, J=2.8, H_(aryl)), 8.76 (s, 1, CH═NAr), 8.71 (d, 1, J=2.8, H_(aryl)), 7.43 (s, 2, Ar: H_(m)), 2.31 (s, 3,Ar: Me).

The sodium salt was cleanly synthesized according to the above general procedure: ¹H NMR (300 MHz, THF-d₈): 3 equiv of THF coordinated.

EXAMPLE 10 [2-Hydroxynaphthyl]—CH═NAr [Ar=2,6-(i-Pr)₂C₆H₃]

The general procedure for imine synthesis was followed using 20.1 g (117 mmol) of 2-hydroxy-1-naphthaldehyde and 24.8 g (140 mmol, 1.20 equiv) of 2,6-diisopropylaniline. A yellow-gold powder (30.8 g, 79.5%) was isolated: ¹H NMR (CDCl₃, 300 MHz, rt) δ 15.30 (d, 1, OH), 9.15 (d, 1, CH═N), 8.08 (d, 1, H_(naphthyl)), 7.98 (d, 1, H_(naphthyl)), 7.88 (d, 1, H_(naphthyl)), 7.60 (t, 1, H_(naphthyl)), 7.45 (t, 1, H_(naphthyl)), 7.35 (m, 3, Ar: H_(m) and H_(p)), 7.29 (d, 1, H_(naphthyl)), 3.20 (septet, 2, CHMe₂), 1.33 (d, 12, CHMe₂).

The sodium salt was cleanly synthesized according to the above general procedure ¹H NMR (300 MHz, THF-d₈): 0.5 equiv of THF coordinated.

EXAMPLE 11 [2-Hydroxynaphthyl]—CH═NAr [Ar=2,6-Me₂C₆H₃]

The general procedure for imine synthesis was followed using 33.7 g (196 mmol) of 2-hydroxy-1-naphthaldehyde and 28.4 g (235 mmol, 1.20 equiv) of 2,6-dimethylaniline. A golden yellow powder (47.2 g, 87.5%) was isolated: ¹H NMR (CDCl₃, 300 MHz, rt, OH resonance not assigned) 5 9.23 (d, 1, N═CH), 8.4-7.1 (m, 9, H_(aryl)), 2.41 (s, 6, Ar: Me).

The sodium salt was cleanly synthesized according to the above general procedure: ¹H NMR (300 MHz, THF-d₈): 0.5 equiv of THF coordinated.

EXAMPLE 12 [2-(OH)-3,5-Cl₂C₆H₂]—CH═NAr [Ar=2,6-(i-Pr)₂C₆H₃]

The general procedure for imine synthesis was followed using 8.67 g (45.4 mmol) of 3,5-dichloro-2-hydroxybenzaldehyde and 9.66 g (54.5 mmol, 1.20 equiv) of 2,6-diisopropylaniline. A light yellow powder (10.7 g, 67.3%) was isolated: ¹H NMR (CDCl₃, 300 MHz, rt) δ 13.95 (s, 1, OH), 8.20 (s, 1, CH═NAr), 7.50 (d, 1, H_(aryl)), 7.18-6.83 (m, 3, H_(aryl)), 7.23 (d, 1, H_(aryl)), 2.89 (septet, 2, CHMe₂), 1.16 (d, 12, CHMe₂); ¹³C NMR (CDCl₃, 75 MHz, rt) δ 165.1 (N═CH), 156.1, 145.0, 138.7, 132.9, 129.8, 128.6, 126.2, 123.4, 123.0 and 119.7 (C_(aryl)), 28.3 (CHMe₂), 23.6 (CHMe₂).

The sodium salt was cleanly synthesized according to the above general procedure: ¹H NMR (300 MHz, THF-d₈)g: 0.5 equiv of THF coordinated.

EXAMPLE 13 [2-(OH)-3,5-Cl₂C₆H₂]—CH═NAr [Ar=2,6-Me₂C₆H₃]

The general procedure for imine synthesis was followed using 16.2 g (85.0 mmol) of 3,5-dichloro-2-hydroxybenzaldehyde and 11.3 g (93.5 mmol, 1.10 equiv) of 2,6-dimethylaniline. A yellow powder (18.2 g, 72.7%) was isolated: ¹H NMR (CDCl₃, 300 MHz, rt) δ 14.15 (s, 1, OH), 8.43 (s, 1, N═CH), 7.65 (d, 1, J=2.5, H_(aryl)), 7.41 (d, 1, J=2.5, H_(aryl)), 7.30-7.18 (m, 3, Ar: H_(m) and H_(p)), 2.35 (s, 6, Me).

The sodium salt was cleanly synthesized according to the above general procedure: ¹H NMR (300 MHz, THF-d₈): 0.33 equiv of THF coordinated.

EXAMPLE 14 [2-(OH)-5-(NO₂)C₆H₂]—CH═NAr [Ar=2,6-(i-Pr)₂C₆H₃]

The general procedure for imine synthesis was followed using 5.22 g (31.2 mmol) of 5-nitro-2-hydroxybenzaldehyde and 6.65 g (37.5 mmol, 1.20 equiv) of 2,6-diisopropylaniline. A yellow powder (4.39 g, 43.1%) was isolated: ¹H NMR (CDCl₃, 300 MHz, rt, OH resonance not assigned) 8 8.38 (s, 1, CH═NAr), 8.35 (d,. 1, J=3, H′_(m) to hydroxy), 8.30 (dd, 1, J=9, 3, H_(m) to hydroxy), 7.23 (s, 3, Ar: H_(m) and H_(p)), 7.15 (d, 1, J=9, H_(o) to hydroxy), 2.93 (septet, 2, CHMe₂), 1.20 (s, 12, CHMe₂).

The sodium salt was cleanly synthesized according to the above general procedure: ¹H NMR (300 MHz, THF-d₈): 0.25 equiv of THF coordinated.

EXAMPLE 15 Pyrrole-2-(CH═NAr) [Ar=2,6-(i-Pr)₂C₆H₃]

The general procedure for imine synthesis was followed using 5.00 g (52.6 mmol) of pyrrole-2-carboxaldehyde and 10.3 g (57.9 mmol, 1.1 equiv) of 2,6-diisopropylaniline. The compound was isolated as an off-white powder: ¹H NMR (CDCl₃, 300 MHz, rt) 8 10.96 (s, 1, NH), 8.05 (s, 1, N═CH), 7.26 (s, 3, Ar: H_(m), H_(p)), 6.68, 6.29 and 6.24 (m, 1 each, H_(pyrrole)), 3.17 (septet, 2, J=6.9, CHMe₂), 1.20 (d, 12, J=7.2, CHMe₂); ¹³C NMR (CDCl₃, 75 MHz, rt) δ 152.6 (N═CH), 148.5, 138.9 and 129.9 (pyrrole: C_(ipso); Ar: C_(ipso), C_(o)), 124.5, 124.0, 123.2, 116.5 and 109.9 (pyrrole: 3 CH carbons and Ar: C_(m), C_(p)), 27.9 (CHMe₂), 23.6 (CHMe₂).

The sodium salt was cleanly synthesized according to the above general procedure: ¹H NMR (300 MHz, C₆D₆/THF-d₈): 1 equiv of THF coordinated.

EXAMPLE 16 (Ar) (H)N—C(Me)═CH—C(O)OMe [Ar=2,6-(i-Pr)₂C₆H₃]

Concentrated HCl (2 drops) was added to a solution of methylacetoacetate (5.2 mL; 48.5 mmol) and 2,6-diisopropylaniline (8.58 g, 48.5 mmol) in methanol. The reaction mixture was stirred at room temperature for 30 h. The product (5.95 g; 45% yield; mp 125-127° C.) was filtered, washed with a small amount of methanol, and then dried under vacuum. Additional product (3.79 g, 28%; mp 115-122° C.) was isolated from the mother liquor: ¹H NMR (300 MHz, CDCl₃, rt): δ 9.78 (br s, 1, NH), 7.29 (t, 1, J=8.1, Ar: H_(p)), 7.17 (d, 2, J=8.2, Ar: H_(m)), 4.71 (s, 1, ═CH), 3.70 (s, 3, OMe), 3.10 (septet, 2, J=6.8, CHMe₂), 1.61 (s, 3, =CMe), 1.22 (d, 6, J=6.8, CHMeMe′), 1.1.5 (d, 6, J=6.7, CHMeMe′).

The sodium salt was cleanly synthesized according to the above general procedure: ¹H NMR (300 MHz, THF-d₈): no THF coordinated.

EXAMPLES 17-40 Synthesis of Nickel Complexes

General Synthesis of Nickel Allyl Initiators. A mixture of two equiv of the appropriate anionic ligand and one equiv of [(allyl)Ni(μ-X)]₂ (X=Cl or Br) was dissolved in THF. The reaction mixture was stirred for several h before being filtered. The solvent was removed in vacuo to yield the desired product. Depending on the solubility of the product, further purification was often carried out by dissolving the product in Et₂O or pentane and filtering again or washing the product with Et₂O or pentane. Due to ease of characterization and, especially, ease of initiation in the presence of a Lewis acid, typically allyl=(a) H₂CC(CO₂Me)CH₂. However, other allyl derivatives were also synthesized and their polymerization activity explored; these include allyl=(b) H₂CCHCH₂, (c) H₂CCHCHMe, (d) H₂CCHCMe₂, (f) H₂CCHCHCl, and (g) H₂CCHCHPh. The [(allyl)Ni(μ-X)]₂ precursors were synthesized according to the procedures published in the following reference: Wilke, G.; Bogdanovic, B.; Hardt, P.; Heimbach, P; Keim, W.; Kroner, M.; Oberkirch, W.; Tanaka, K.; Steinrucke, E.; Walter, D.; Zimmermann, H. Angew. Chem. Int. Ed. Engl. 1966, 5, 151-164.

Complexes 1-20 were synthesized according to the above general procedure and their structures, syntheses and characterization follow:

EXAMPLE 17

Complex 1a. Two equiv (610 mg, 1.35 mmol) of the sodium salt of the ligand were reacted with one equiv (321 mg, 0.674 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 655 mg (82.6% yield) of a deep purple powder.

EXAMPLE 18

Complex 1d. Two equiv (667 mg, 1.47 mmol) of the sodium salt of the ligand were reacted with one equiv (306 mg, 0.737 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CCHCMe₂) to give a purple solid: ¹H NMR (C₆D₆, 300 MHz, rt, H₂CCHCMe₂ resonances not assigned) δ 7.25-6.79 (m, 6, H_(aryl)), 4.93 (t, 1, J=4.6, ArNHC═CH—), 4.56 (br m, 1, H₂CCHCMe₂), 3.48 (septet, 2, J=6.9, CHMe₂), 2.99 (septet, 2, J=6.9, C′HMe₂), 2.07 (m, 2, Cy: CH₂), 1.92 (m, 2, Cy: CH₂), 1.42 (m, 2, Cy: CH₂), 1.2-1.1 (doublets, 24, CHMe₂, C′HMe₂), 0.72 and 0.61 (br s, 3 each, H₂CCHCMeMe′).

EXAMPLE 19

Complex 2a. Two equiv (1.08 g, 2.44 mmol) of the lithium salt of the ligand were reacted with one equiv (581 mg, 1.22 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to yield 1.35 g (93.8% yield) of a red powder. ¹H NMR spectrum in C₆D₆ is complex.

EXAMPLE 20

Complex 3a. Two equiv (4.01 g, 8.71 mmol) of the sodium salt of the ligand were reacted with one equiv (2.07 g, 4.35 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to yield 3.61 g (75.2% yield) of a golden yellow powder. ¹H NMR (C₆D₆, 300 MHz, rt) δ 7.84 (s, 1, N═CH), 7.44 and 6.92 (d, 1 each, H_(aryl)), 7.20 (m, 3, Ar: H_(m), H′_(m) and H_(p)), 3.88 (d, 1, HH′CC(CO₂Me)CHH′), 3.86 (septet, 1, CHMe₂), 3.80 (s, 3, OMe), 3.04 (septet, 1, C′HMe₂), 2.91 (s, 1, HH′CC(CO₂Me)CHH′), 1.89 (m, 1, HH′CC(CO₂Me)CHH′), 1.43 (s, 1, HH′CC(CO₂Me)CHH′), 1.41 and 1.25 (s, 9 each, CMe₃ and C′Me₃), 1.37, 1.27, 1.16 and 1.02 (d, 3 each, CHMeMe′ and C′HMeMe′); ¹³C NMR (CD₂Cl₂, 75 MHz, rt) δ 166.6 (N═CH), 167.4, 164.7, 153.0, 141.3, 140.9, 139.9, 136.5, 117.7 and 110.9 (H₂CC(CO₂Me)CH₂; Ar: C_(ipso), C_(o), C′_(o); Ar′: C_(ipso), C_(o), C_(m), C′_(m)), 130.2, 127.9, 126.8, 124.0 and 123.9 (Ar: C_(m), C′_(m), C_(p); Ar′: Cp and C′_(o)), 59.8 and 47.0 (H₂CC(CO₂Me)CH₂), 53.1 (CO₂Me), 35.9 and 34.3 (CMe₃ and C′Me₃), 31.6 and 30.0 (CMe₃ and C′Me₃), 29.0, 28.5, 25.7, 25.6, 23.3 and 22.7 (CHMeMe′ and C′HMeMe′).

Single crystals were formed by cooling a pentane solution of the complex to −35° C. in the drybox freezer. The structure of the compound was solved by X-ray crystallography and is in agreement with the proposed structure.

EXAMPLE 21

Complex 4a. Two equiv (834 mg, 2.11 mmol) of the sodium salt of the ligand were reacted with one equiv (501 mg, 1.05 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 935 mg (89.7% yield) of a golden yellow powder: ¹H NMR (THF-d_(8, 300) MHz, rt) δ 7.94 (s, 1, N═CH), 7.40 (d, 1, H_(aryl)), 7.13-6.92 (m, 3, Ar: H_(m), H′_(m), H_(p)), 7.00 (d, 1, H_(aryl)), 3.78 (s, 3, OMe), 3.76 (d, 1, HH′CC(CO₂Me)CHH′), 2.80 (s, 1, HH′CC(CO₂Me)CHH′), 2.45 (s, 3, Ar: Me), 2.10 (s, 3, Ar: Me′), 1.85 (d, 1, HH′C(CO₂Me)CHH′), 1.60 (t, 1, HH′CC(CO₂Me)CHH′), 1.40 and 1.24 (s, 9 each, CMe₃ and C′Me₃); ¹³C NMR (CD₂Cl₂, 75 MHz, rt) δ 166.2 (N═CH), 167.3, 164.3, 155.1, 141.1, 136.2, 130.0, 129.4, 118.0 and 110.3 (H₂CC(CO₂Me)CH₂, Ar: C_(ipso), C_(o), C′_(o); Ar′: C_(ipso), C_(o), C_(m), C′_(m)), 129.8, 128.5, 128.4, 127.8 and 125.6 (Ar: C_(m), C′_(m), C_(p); Ar′: C_(p), C′_(o)), 57.8 and 47.7 (H₂CC(CO₂Me)CH₂), 52.8 (OMe), 35.7 and 34.1 (CMe₃ and C′Me₃), 31.4 and 29.4 (CMe₃ and C′Me₃), 19.0 and 18.4 (Ar: Me and Me′).

EXAMPLE 22

Complex 5a. Two equiv (390 mg, 0.709 mmol) of the sodium salt of the ligand were reacted with one equiv (169 mg, 0.355 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl H₂CC(CO₂Me)CH₂) to give 189 mg (45.8% yield) of a golden yellow powder: ¹H NMR (CDCl₃, 300 MHz, rt, broad resonances) δ 7.80 (br s, 1, N═CH), 7.50 (br s, 1, H_(aryl)), 7.42 (br s, 1, Ar: H_(m), H′_(m)), 6.96 (br s, 1, H_(aryl)), 3.92 (br s, 1, HH′CC(CO₂Me)CHH′), 3.86 (br s, 3, OMe), 2.84 (br s, 1, HH′CC(CO₂Me)CHH′), 1.98 and 1.76 (br s, 1 each, HH′CC(CO₂Me)CHH′), 1.43 and 1.29 (br s, 9 each, CMe₃ and C′Me₃).

EXAMPLE 23

Complex 6a. Two equiv (900 mg, 2.10 mmol) of the sodium salt of the ligand were reacted with one equiv (500 mg, 1.05 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 864 mg (77.9% yield) of a golden yellow powder: ¹H NMR (C₆D₆, 300 MHz, rt) δ 8.40 (d, 1, J=3.0, H_(aryl)), 7.66 (d, 1, J=3.0, H_(aryl)), 7.12 (s, 1, N═CH), 7.10-6.90 (m, 3, Ar: H_(m), H′_(m), H_(p)), 4.05 (m, 1, HH′CC(CO₂Me)CHH′), 3.49 (septet, 1, J=6.9, CHMe₂), 3.21 (s, 3, OMe), 2.96 (septet, 1, J=6.8, C′HMe₂), 2.67 (s, 1, HH′CC(CO₂Me)CHH′), 2.23 (m, 1, HH′CC(CO₂Me)CHH′), 1.34 (br s, 1, HH′CC(CO₂Me)CHH′), 1.36, 1.15, 0.95 and 0.84 (d, 3 each, J=6.8, CHMeMe′, C′HMeMe′).

EXAMPLE 24

Complex 6f. Two equiv (267 mg, 0.621 mmol) of the sodium salt of the ligand were reacted with one equiv (105 mg, 0.310 mmol) of [(allyl)Ni(μ-Cl)]₂ (allyl=H₂CCHCHCl) to give 245 mg (78.3% yield) of a golden yellow powder: ¹H NMR spectrum in C₆D₆ is complex.

EXAMPLE 25

Complex 7a. Two equiv (926 mg, 1.49 mmol) of the sodium salt of the ligand were reacted with one equiv (354 mg, 0.745 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 861 mg (94.4% yield) of a golden yellow powder: ¹H NMR (C₆D₆, 300 MHz, rt) δ 8.43 (d, 1, J=2.6, H_(aryl)), 7.81 (d, 1, J=2.9, H_(aryl)), 7.48 (s, 2, Ar: H_(m)), 7.45 (s, 1, N═CH), 4.12 (d, 1, J=2.9, HH′C(CO₂Me)CHH′), 3.28 (s, 3, OMe), 2.84 (s, 1, HH′C(CO₂Me)CHH′), 2.44 (t, 1, J=2.4, HH′C(CO₂Me)CHH′), 1.58, 1.41 and 1.28 (s, 9 each, CMe₃, C′Me₃, C″Me₃), 1.31 (d, 1, J=1.1, HH′C(CO₂Me)CHH′); ¹³ ¹³C NMR (C₆D₆, 75 MHz, rt) δ 166.4 (N═CH), 165.5, 162.9, 151.0, 148.1, 144.9, 139.4, 138.8, 134.21, 120.5 and 113.4 (H₂CC(CO₂Me)CH₂; Ar: C_(ipso), C_(o), C′_(o), C_(p); Ar′: C_(ipso), C_(o), C_(m), C′_(m)), 134.16, 126.1, 125.1 and 124.7 (Ar: C_(m), C′_(m) and Ar′: C_(p) and C′_(o)), 63.3 and 49.0 (H₂C(CO₂Me)CH₂), 52.4 (OMe), 37.2 (CMe₃), 34.8, 34.4 and 31.4 (CMe₃, C′Me₃ and C″Me₃), (C′Me₃ and C″Me₃ overlap with CMe₃ or CMe₃ or C′Me₃ resonances).

EXAMPLE 26

Complex 8a. Two equiv (529 mg, 1.49 mmol) of the sodium salt of the ligand were reacted with one equiv (354 mg, 0.745 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 662 mg (94.1% yield) of a golden yellow powder: ¹H NMR (CD₂Cl_(2, 300) MHz, rt) δ 8.80 (d, 1, H_(aryl)), 8.40 (d, 1, H_(aryl)), 8.08 (s, 1, N═CH), 7.14 (m, 3, Ar: H_(m), H′_(m), H_(p)), 3.82 (d, 1, HH′CC(CO₂Me)CHH′), 3.88 (s, 3, OMe), 3.00 (s, 1, HH′C(CO₂Me)CHH′), 2.46 (s, 3, Ar: Me), 2.16 (m, 1, HH′CC(CO₂Me)CHH′), 2.14 (s, 3, Ar: Me′), 1.91 (m, 1, HH′CC(CO₂Me)CHH′).

EXAMPLE 27

Complex 9a. Two equiv (1.46 g, 2.09 mmol) of the sodium salt of the ligand were reacted with one equiv (497 mg, 1.05 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 1.42 g (96.0% yield) of a red powder: ¹H NMR (CD₂Cl₂, 300 MHz, rt) δ 8.79 (d, 1, H_(aryl)), 8.44 (d, 1, H_(aryl)), 8.06 (s, 1, N═CH), 7.51 and 7.49 (s, 1 each, Ar: H_(m), H′_(m)), 3.96 (d, 1, HH′CC(CO₂Me)CHH′), 3.85 (s, 3, OMe), 3.65 (br s, ˜1.25 equiv THF), 3.00 (s, 1, HH′CC(CO₂Me)CHH′), 2.37 (s, 3, Ar: Me), 2.23 (m, 1, HH′CC(CO₂Me)CHH′), 2.13 (s, 1, HH′CC(CO₂Me)CHH′), 1.85 (br s, 1.25 equiv THF); ¹³C NMR (CD₂Cl₂, 75 MHz, rt) δ 168.3 (N═CH), 166.0, 163.6, 148.9, 142.7, 140.5, 134.3, 122.0, 117.3, 116.7 and 114.8 (H₂CC(CO₂Me)CH₂; Ar: C_(ipso), C_(o), C′_(o), C_(p); Ar′: C_(ipso), C_(o), C_(m), C′_(m)), 136.1, 133.5, 133.5 and 126.3 (Ar: C_(m), C′_(m); Ar′: C_(p), C′_(o)); 72.6 (br, THF), 61.2 and 51.4 (H ₂CC(CO₂Me)CH₂), 53.6 (OMe), 34.9 (br, THF), 20.8 (Ar: Me).

EXAMPLE 28

Complex 10a. Two equiv (490 mg, 1.3 mmol) of the sodium salt of the ligand were reacted with one equiv (300 mg, 0.63 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 259 mg (41% yield) of a yellow-green powder. About 12.5% of the isolated sample consists of a second species whose NMR spectrum is consistent with a (ligand)₂Ni(II) complex. The remainder is the allyl complex: ¹H NMR (C₆D₆, 300 MHz, rt) δ 8.75 (s, 1, N═CH), 7.50-6.90 (m, 8, H_(aryl)), 6.03 (d, 1, J=9.2, H_(aryl)), 4.16 (d, 1, J=3.0, HH′CC(CO₂Me)CHH′), 3.92 (septet, 1, J=6.9, CHMe₂), 3.33 (s, 3, OMe), 3.27 (septet, 1, J=6.8, C′HMe₂), 2.83 (s, 1, HH′CC(CO₂Me)CHH′), 2.77 (dd, 1, J=3.4, 1.6, HH′CC(CO₂Me)CHH′), 1.47 (dd, 1, J=1.5, 0.9, HH′CC(CO₂Me)CHH′), 1.36, 1.20, 1.02 and 0.92 (d, 3 each, J=6.5-6.8, CHMeMe′, C′HMeMe′). [Proposed (ligand)₂Ni(II) complex: δ 8.19 (s, 2, N═CH), 7.50-6.90 (m, 16, H_(aryl)), 6.12 (d, 2, H_(aryl)), 4.54 (septet, 4, J=6.98, CHMe₂), 1.53 (d, 12, J=6.8 CHMeMe′), 1.18 (d, 12, CHMeMe′).]

EXAMPLE 29

Complex 11a. Two equiv (487 mg, 1.32 mmol) of the sodium salt of the ligand were reacted with one equiv (314 mg, 0.660 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 351 mg (61.5% yield) of a yellow-green powder. About 17% of the isolated product consists of a second species whose NMR spectrum is consistent with a (ligand)₂Ni(II) complex; the remainder is the allyl complex: ¹H NMR (C₆D₆, 300 MHz, rt) δ 8.64 (s, 1, N═CH), 7.41-6.93 (m, 8, H_(aryl)), 6.05 (d, 1, J=9.2, H_(aryl)), 4.07 (d, 1, J=3.3, HH′CC(CO₂Me)CHH′), 3.30 (s, 3, OMe), 2.65 (s, 1, HH′CC(CO₂Me)CHH′), 2.28 (s, 3, Ar: Me), 2.16 (s, 4, Ar: Me′ and HH′CC(CO₂Me)CHH′), 1.41 (br s, 1, HH′CC(CO₂Me)CHH′. [Proposed (ligand)₂Ni complex: δ 8.01 (s, 2, N═CH), 2.66 (s, 12, Ar: Me).]

EXAMPLE 30

Complex 11b. Two equiv (179 mg, 0.484 mmol) of the sodium salt of the ligand were reacted with one equiv (101 mg, 0.242 mmol) of [(allyl)Ni(g-Br)]₂ (allyl=H₂CCHCMe₂) to give an orange-yellow powder (176 mg, 90.4%): ¹H NMR (C₆D₆, 300 MHz, rt) δ 8.65 (s, 1, N═CH), 7.48-6.94 (m, 9, H_(aryl)), 5.14 (dd, 1, J=13.0, 7.9, H₂CCHCMe₂), 2.34 (s, 3, Ar: Me), 2.08 (s, 3, Ar: Me′), 1.40 (d, 1, J=7.7, HH′CCHCMe₂), 1.36 (d, 1, J=13.1, HH′CCHCMe₂), 1.13 and 1.02 (s, 3 each, H₂CCHCMeMe′).

EXAMPLE 31

Complex 12a. Two equiv (862 mg, 2.11 mmol) of the sodium salt of the ligand were reacted with one equiv (501 mg, 1.05 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl H₂CC(CO₂Me)CH₂) to give 951 mg (88.8% yield) of a yellow-green powder. About 10% of the isolated product consists of a second species whose NMR spectrum is consistent with a (ligand)₂Ni(II) complex; the remainder is the allyl complex: ¹H NMR (C₆D₆, 300 MHz, rt) δ 7.40 (s, 1, N═CH), 7.38-6.98 (m, 5, H_(aryl)), 4.13 (d, 1, J=2.9, HH′CC(CO₂Me)CHH′), 3.61 (septet, 1, J=6.9, CHMe₂), 3.27 (s, 3, OMe), 3.03 (septet, 1, J=6.8, C′HMe₂), 2.78 (s, 1, HH′CC(CO₂Me)CHH′), 2.16 (t, 1, J=1.7, HH′CC(CO₂Me)CHH′), 1.38 (br s, 1, HH′CC(CO₂Me)CHH′), 1.34, 1.16, 0.94 and 0.83 (d, 3 each, J=6.6-7.0, CHMeMe′, C′HMeMe′); ¹³ ¹³C NMR (C₆D₆, 75 MHz, rt, diagnostic resonances) δ 165.2 (N═CH), 61.9 and 48.7 (H₂CC(CO₂Me)CH₂), 52.3 (OMe), 28.7 and 28.4 (CHMe₂; C′HMe₂), 25.3, 25.3, 22.8 and 22.6 (CHMeMe′, C′HMeMe′). [Proposed (ligand)₂Ni complex: 1H NMR (C₆D₆) 8 7.20-6.36 (m, 12, N═CH and H_(aryl)), 4.49 (septet, 4, J=6.9, CHMe₂), 1.42 and 1.13 (d, 12 each, J=7.0, CHMeMe′); ¹³ ¹³C NMR (C₆D₆) δ 29.6: (CHMe₂), 24.4 and 23.6 (CHMeMe′).]

EXAMPLE 32

Complex 13a. Two equiv (491 mg, 1.26 mmol) of the sodium salt of the ligand were reacted with one equiv (300 mg, 0.632 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl H₂CC(CO₂Me)CH₂) to give 469 mg (-82.4% yield) of a green powder. 13% of the isolated product consists of a second species whose NMR spectrum is consistent with a (ligand)₂Ni(II) complex; the remainder is the allyl complex: ¹H NMR (C₆D₆, 300 MHz, rt) δ 7.37 (d, 1, J=2.6, H_(aryl)), 6.98 (s, 1, N═CH), 6.98-6.86 (m, 3, H_(aryl)), 6.56 (d, 1, J=2.0, H_(aryl)), 4.05 (d, 1, J=2.6, HH′CC(CO₂Me)CHH′), 3.23 (s, 3, OMe), 2.60 (s, 1, HH′CC(CO₂Me)CHH′, overlaps with Ar: Me of dimer), 2.09 and 2.03 (s, 3 each, Ar: Me, Me′), 2.06 (m, 1, HH′CC(CO₂Me)CHH′), 1.31 (s, 1, HH′CC(CO₂Me)CHH′). [Proposed (ligand)₂Ni(II) complex: δ 2.60 (s, Ar: Me).]

EXAMPLE 33

Complex 14a. Two equiv (772 mg, 2.11 mmol) of the sodium salt of the ligand were reacted with one equiv (501 mg, 1.05 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 891 mg (87.4% yield) of a yellow-orange powder: ¹H NMR (CD₂Cl₂, 300 MHz, rt) δ 8.25 (d, 1, Ar′: H_(o)), 8.16 (dd, 1, Ar′: H_(p)), 7.98 (s, 1, N═CH), 7.24 (m, 3, Ar: H_(m), H′_(m), H_(p)), 6.90 (d, 1, Ar′: H_(m)), 3.92 (d, 1, HH′CC(CO₂Me)CHH′), 3.86 (s, 3, OMe), 2.99 (septet, 1, CHMe₂), 3.02 (s, 1, HH′CC(CO₂Me)CHH′), 2.98 (septet, 1, C′HMe₂), 2.08 (m, 1, HH′CC(CO₂Me)CHH′), 1.66 (t, 1, HH′CC(CO₂Me)CHH′), 1.39, 1.31, 1.17 and 1.01 (d, 3 each, CHMeMe′ and C′HMeMe′).

EXAMPLE 34

Complex 15a. Two equiv (1.09 g, 3.13 mmol) of the sodium salt of the ligand were reacted with one equiv (743 mg, 1.56 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 858 mg (66.7% yield) of a yellow-orange powder: ¹H NMR (C₆D₆, 300 MHz, rt) δ 7.20-7.00 (m, 5, N═CH; Ar: H_(m), H′_(m), H_(p); H_(pyrrole)), 6.77 (m, 1, H_(pyrrole)), 6.42 (m, 1, H_(pyrrole)), 3.84 (m, 1, HH′CC(CO₂Me)CHH′), 3.65 (septet, 1, J=6.8, CHMe₂), 3.30 (s, 3, OMe), 3.19 (septet, 1, J=6.9, C′HMe₂), 2.85 (m, 1, HH′CC(CO₂Me)CHH′), 2.20 (d, 1, J=0.89, HH′CC(CO₂Me)CHH′), 1.89 (d, 1, J=0.89, HH′CC(CO₂Me)CHH′), 1.24, 1.18, 1.05 and 0.92 (d, 3 each, J=6.8-7.1, CHMeMe′, C′HMeMe′); ¹³C NMR (C₆D₆, 75 MHz, rt) δ 162.5 (N═CH), 166.2, 148.7, 141.5, 141.4, 141.3, 140.8, 126.5, 123.43, 123.39, 118.8, 114.0 and 109.6 (H₂CC(CO₂Me)CH₂); C_(aryl); C_(pyrrole)), 54.0 and 50.3 (H₂CC(CO₂Me)CH₂), 52.1 (OMe), 28.4 and 28.3 (CHMe₂, C′HMe₂), 25.1, 24.9, 23.0 and 22.5 (CHMeMe′ and C′HMeMe′).

EXAMPLE 35

Complex 16a. Two equiv (323 mg, 2.15 mmol) of the sodium salt of the ligand were reacted with one equiv (511 mg, 1.07 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 322 mg (62.6% yield) of an off-white (slightly red) powder.

EXAMPLE 36

Complex 17a. Two equiv (987 mg, 3.32 mmol) of the sodium salt of the ligand were reacted with one equiv (789 mg, 1.66 mmol) of [(allyl)Ni(4-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 1.14 g (79.4% yield) of a bright yellow-orange powder: ¹H NMR (C₆D₆, 300 MHz, rt) δ 7.06 (br s, 3, H_(aryl)), 4.86 (d, 1, J=1.2, ArNC(Me)CHCO₂Me), 4.04 (septet, 1, J=6.7, CHMe₂), 3.90 (d, 1, J=3.0, HH′CC(CO₂Me)CHH′), 3.37 and 3.36 (s, 3 each, (OMe)allyl and (OMe)ligand), 3.24 (septet, 1, J=7.0, C′HMe₂), 2.66 (s, 1, HH′CC(CO₂Me)CHH′), 2.01 (m, 1, HH′CC(CO₂Me)CHH′), 1.44 (s, 3, ArNC(Me)CHCO₂Me), 1.36, 1.29, 1.17 and 1.03 (d, 3 each, J=6.2-6.9, CHMeMe′, C′HMeMe′), 1.14 (br s, 1, HH′ CC(CO₂Me)CHH′); ¹³C NMR (C₆D₆, 75 MHz, rt) δ 170.5, 169.4, 166.7, 151.5, 147.3, 141.1, 140.1, 125.4, 123.7 and 109.2 (Ar: C_(ipso), C_(o), C_(o)′, C_(m), C_(m)′, C_(p); H₂CC(CO₂Me)CH₂; ArNC(Me)CHCO₂Me), 80.2 (ArNC(Me)CHCO₂Me), 60.8 and 46.3 (H₂CC(CO₂Me)CH₂), 52.0 and 50.9 (H₂CC(CO₂Me)CH₂, ArNC(Me)CHCO₂Me), 28.4 and 28.1 (CHMe₂, C′HMe₂), 24.5, 24.3, 24.3 and 23.6 (CHMeMe′, C′HMeMe′), 23.2 (ArNC(Me)CHCO₂Me).

EXAMPLE 37

Complex 18a. Two equiv (1.20 g, 2.14 mmol) of the thallium salt of the ligand were reacted with one equiv (508 mg, 1.07 mmol) of [(allyl)Ni(μ-Br)]2 (allyl=H₂CC(CO₂Me)CH₂) to give 730 mg (72.2% yield) of a red powder: H NMR spectrum in C₆D₆ is complex.

EXAMPLE 38

Complex 19a. Two equiv (435 mg, 1.03 mmol) of the potassium salt of the ligand were reacted with one equiv (245 mg, 0.514 mmol) of [(allyl)Ni(μ-Br)]2 (allyl=H₂CC(CO₂Me)CH₂) to give 309 mg (60.4% yield) of a golden yellow powder. Some impurities are present, but the majority of the product is the allyl complex: ¹H NMR (CD₂Cl₂, 300 MHz, rt) δ 7.44 (s, 2, H_(pyrazole)), 7.4-7.0 (m, 10, H_(aryl)), 6.00 (s, 2, H_(pyrazole)), 3.91 (s, 3, OMe), 3.50 (s, 2, HH′CC(CO₂Me)CHH′), 2.96 (septet, 2, J=6.8, CHMe₂), 1.27 (d, 6, J=7.0, CHMeMe′), 1.19 (d, 6, J=7.0, CHMeMe′), 0.90 (s, 2, HH′CC(CO₂Me)CHH′).

EXAMPLE 39

Complex 20a. Two equiv (583 mg, 1.32 mmol) of the sodium salt of the ligand were reacted with one equiv (315 mg, 0.662 mmol) of [(allyl)Ni(μ-Br)]2 (allyl=H₂CC(CO₂Me)CH₂) to give 407 mg (53.6% yield) of a bright yellow-green powder: ¹H NMR (C₆D₆, 300 MHz, rt) δ 7.11 (m, 6, H_(aryl)), 5.04 (s, 1, NC(Me)C(H)C(Me)N), 4.04 (septet, 2, CHMe₂), 3.40 (septet, 2, C′HMe₂), 3.35 (s, 3, OMe), 2.29 (s, 2, HH′CC(CO₂Me)CHH′), 1.95 (s, 2, HH′CC(CO₂Me)CHH′), 1.62 (s, 6, NC(Me)C(H)C(Me)N), 1.38, 1.32, 1.20 and 1.07 (d, 6 each, CHMeMe′, C′HMeMe′).

EXAMPLE 40

Complex 20b. Two equiv (296 mg, 0.672 mmol) of the sodium salt of the ligand were reacted with one equiv (90.8 mg, 0.336 mmol) of [(allyl)Ni(μ-Cl)]2 (allyl=H₂CCHCH₂) to give 151 mg (43.4% yield) of a bright yellow-orange powder: ¹H NMR (C₆D₆, 300 MHz, rt) δ 7.14-7.02 (m, 6, H_(aryl)), 5.84 (m, 1, H₂CCHCH₂), 5.04 (s, 1, NC(Me)C(H)C(Me)N), 4.05 (septet, 2, J=6.9, CHMe₂), 3.43 (septet, 2, J=6.9, C′HMe₂), 1.79 (d, 2, J=12.8, HH′CCHCHH′), 1.64 (s, 6, NC(Me)C(H)C(Me)N), 1.53 (d, 2, J=6.8, HH′CCHCHH′), 1.39 1.29, 1.21 and 1.10 (d, 6 each, J=6.8-7.1, CHMeMe′, C′HMeMe′)

EXAMPLES 41-130

Ethylene and Propylene Polymerization Procedures and Reactions

The results of ethylene and propylene polymerizations catalyzed by complexes 1-20 under various reaction conditions (see general procedures and Table 1 below) are reported in Tables 2-5. The polymers were characterized by NMR, GPC, and DSC analysis. A description of the methods used to analyze the amount and type of branching in polyethylene samples by ¹³C NMR spectroscopy is given in WO Pat. Appl. 96/23010. GPC's were run in trichlorobenzene at 135° C. and calibrated against polystyrene standards.

General Procedure for the Screening of Ethylene Polymerizations by Nickel Allyl Initiators at 6.9 MPa Ethylene

In the drybox, a glass insert was loaded with the isolated allyl initiator. The insert was cooled to −35° C. in the drybox freezer, 5 mL of solvent (typically C₆D₆ or CDCl₃) was added to the cold insert, and the insert was cooled again. A Lewis acid cocatalyst [typically BPh₃ or B(C₆F₅)₃] was often added to the cold solution, and the insert was then capped and sealed. Outside of the drybox, the cold tube was placed under ethylene (typically 6.9 MPa) and allowed to warm to rt as it was shaken mechanically for approximately 18 h. An aliquot of the solution was used to acquire a ¹H NMR spectrum. The remaining portion was added to ˜20 mL of MeOH in order to precipitate the polymer. The polyethylene was isolated and dried under vacuum.

General Procedure for the Screening of Ethylene Polymerizations by Nickel Allyl Initiators at 28-35 kPa Ethylene with Polymethylaluminoxane (PMAO) Cocatalyst

In the drybox, the nickel complex was placed in a Schlenk flask and dissolved in ˜20 mL of toluene. The flask was sealed, removed from the drybox and attached to an ethylene line where it was purged with first nitrogen and then ethylene. After purging with ethylene, PMAO was quickly added to the reaction mixture and the flask was placed under 28-35 kPa of ethylene. After being stirred overnight, the reaction mixture was quenched with 15 mL of a solution of concentrated HCl in methanol (10:90 volume percent solution). The polymer was collected on a frit, washed with methanol and then acetone and then dried in vacuo overnight.

General Procedure for the Screening of Propylene Polymerization by Nickel Allyl Initiators at 48 kPa Propylene with Polymethylaluminoxane (PMAO) Cocatalyst

In the drybox, the nickel complex was placed in a Schlenk flask and dissolved in ˜10 mL of toluene. The flask was sealed, removed from the drybox and attached to an ethylene line where it was purged with first nitrogen and then propylene. After purging with propylene, PMAO was quickly added to the reaction mixture and the flask was placed under ˜48 kPa of propylene. After being stirred overnight, the reaction mixture was quenched with ˜10 mL of a solution of concentrated HCl in methanol (10:90 volume percent solution). The polymer was collected on a frit, washed with methanol and then acetone and then dried in vacuo overnight.

General Procedure for the Screening of Propylene Polymerization by Nickel Allyl Initiators at 48 kPa Propylene with B(C₆F₅)₃ Cocatalyst

In the drybox, the nickel complex was placed in a Schlenk flask and dissolved in ˜10 mL of CH₂Cl₂. Two equiv of B(C₆F₅)₃ were dissolved in a minimal amount of CH₂Cl₂ and the solution was transferred to the Schlenk flask. The flask was sealed, removed from the drybox and attached to an ethylene line where it was purged with first nitrogen and then propylene. The flask was placed under ˜48 kPa of propylene and the reaction mixture was stirred overnight and then was quenched with ˜10 mL of a solution of concentrated HCl in methanol (10:90 volume percent solution). The polymer was collected on a frit, washed with methanol and then acetone and then dried in vacuo overnight

General Procedure for the Screening of Propylene Polymerization by Nickel Allyl Initiators at 600 kPa Propylene With B(C₆F₅)₃ Cocatalyst

In the drybox, the nickel complex was placed in a vessel and dissolved in ˜20 mL of CH₂Cl₂. Two equiv of B(C₆F₅)₃ were dissolved in ˜10 mL of CH₂Cl₂ and placed in a separate vessel. Both vessels were sealed and removed from the drybox. The solution of the nickel complex was transferred to a 100 mL Parr reactor under vacuum and the solution of B(C₆F₅)₃ was transferred to the addition port of the same reactor. The B(C₆F₅)₃ solution was forced into the reactor ˜600 kPa of propylene. The reactor pressure was maintained at 600 kPa and the reaction mixture was stirred for 3 h. Next, the reaction mixture was quenched with ˜10 mL of a solution of concentrated HCl in methanol (10:90 volume percent solution). If polymer was present, it was collected on a frit, washed with methanol and then acetone and then dried in vacuo overnight. Oligomers were characterized by GC analysis.

TABLE 1 Reaction Conditions Used in Ethylene and Propylene Polymerizations^(a) A 5 mL C₆D₆, rt, 18 h, 6.9 MPa E, 2 equiv BPh₃ B 5 mL CDCl₃, 80° C., 18 h, 6.9 MPa E, 1 equiv B(C₆F₅)₃ C 5 mL C₆D₆, 80° C., 18 h, 6.9 MPa E, 2 equiv BPh₃ D 5 mL C₆D₆, rt, 18 h, 6.9 MPa E, 1 equiv B(C₆F₅)₃ E 5 mL C₆D₆, 80° C., 18 h, 6.9 MPa E, 2 equiv B[3,5-C₆H₃—(CF₃)₂]₃ F 5 mL CDCl₃, rt, 18 h, 6.9 MPa E, 2 equiv B[3,5-C₆H₃—(CF₃)₂]₃ G 5 mL CDCl₃, rt, 18 h, 6.9 MPa E, 2 equiv B(C₆F₅)₃ H 5 mL CDCl₃, 80° C., 18 h, 6.9 MPa E, 2 equiv B(C₆F₅)₃ I 20 mL toluene, rt, overnight, 28-35 kPa E, excess PMAO J 10 mL toluene, rt, overnight, 48 kPa P, excess PMAO K 10 mL CH₂Cl₂, rt, overnight, 48 kPa P, 2 equiv B(C₆F₅)₃ L 30 ml CH₂Cl₂, rt, 3 h, 600 kPa P, 2 equiv B(C₆F₅)₃ ^(a)Abbreviations. E: Ethylene; P: Propylene; PMAO: Polymethylaluminoxane.

TABLE 2 Polymerization of Ethylene by Compounds 1-20 at 6.9 MPa Ethylene Conditions A (5 mL C₆D₆, rt, Conditions B (5 mL CDCl₃, 80° C., 18 h, 2 equiv BPh₃) 18 h, 1 equiv B(C₆F₅)₃) Ex. Cmpd^(b) PE (g)^(c) TO^(d) Ex. Cmpd^(b) PE (g)^(c) TO^(d) 41  1a 0.43^(e) 260 61  1a  0.40^(f) 240 42  2a ^(a) ^(a) 62  2a 1.2  730 43  3a 4.1 2400  63  3a ^(a) ^(a) 44  4a 12.7 7500  64  4a ^(a) ^(a) 45  5a 5.1 3000  65  5a ^(a) ^(a) 46  6a 1.3^(g) 590 66  6a 1.09 650 47  7a ^(a) ^(a) 67  7a 0.14  81 48  8a 0.29 170 68  8a 2.65 1600  49  9a 0.70 410 69  9a 2.5  1500  50 10a 0.33 200 70 10a ^(a) ^(a) 51 11a ^(a) ^(a) 71 11a 0.24 140 52 12a 0.15  87 72 12a 0.16  95 53 13a ^(a) ^(a) 73 13a 0.66 390 54 14a 1.1 640 74 14a 1.2  730 55 15a 0.14  80 75 15a 0.21 120 56 16a ^(a) a 76 16a 2.3  1400  57 17a 0.52 310 77 17a 1.33 780 58 18a 0.35 590 78 18a ^(a) ^(a) 59 19a 0.53 310 79 19a ^(a) ^(a) 60 20a 0.14  81 80 20a ^(a) ^(a) ^(a)Less that 0.1 g of polyethylene was isolated. ^(b)0.06 mmol ^(c)PE: Polyethylene. ^(d)TO: number of turnovers per metal center = (moles ethylene consumed, as determined by the weight of the isolated polymer or oligomers) divided by (moles catalyst). ^(e)1 equiv of B(C₆F₅)₃ was used (Conditions D in Table 1). ^(f)5 mL C₆D₆ and 2 equiv BPh₃ were used (Conditions C in Table 1). ^(g)1 equiv BPh₃ was used.

TABLE 3 Characterization of Polyethylenes Produced by Complexes 1-20 Cmpd Tm NMR Analysis Ex. (Conds) Mw Mn PDI (° C.) (Branching per 1000 CH₂) 81 1a(C) 703000  6640 106 ¹H NMR: 16.5 Total Methyls 82 1a(D) 1320000  16100  81.6 ¹³C NMR: 74.0 Total Methyls; Branch Lengths: Methyl (38.7), Ethyl (11.0), Propyl (5.3), Butyl (5.9), Amyl (3), ≧Hex^(b) (4.5), ≧Am^(b) (11.3), ≧Bu^(b) (21.4) 83 1a(E) 259000  6550 39.5   68^(c) ¹H NMR: 54.9 Total Methyls 110 84 2a(B) 21100 2840 7.44 101 ¹³C NMR: 58.4 Total Methyls; Branch Lengths: Methyl (37.5), Ethyl (4.3), Propyl (2.3), Butyl (2), Amyl (2.4), ≧Hex^(b) (9.9), ≧Am^(b) (11.8), ≧Bu^(b) (14.4) 85 3a(A) 120 ¹³C NMR: 27.9 Total Methyls; Branch Lengths: Methyl (21.7), Ethyl (2.4), Propyl (0.5), Butyl (0.7), Amyl (0.4), ≧Hex^(b) (2.6), ≧Am^(b) (2.5), ≧Bu^(b) (3.3) 86 4a(A) ¹³C NMR: 52.0 Total Methyls; Branch Lengths: Methyl (38.0), Ethyl (2.3), Propyl (2.5), Butyl (2.9), Amyl (2.5), ≧Hex^(b) (3.0), ≧Am^(b) (6.0), ≧Bu^(b) (5.4) 87 5a(A) 88600 11100  7.95 ¹³C NMR: 94.7 Total Methyls; Branch Lengths: Methyl (66.7), Ethyl (12.5), Propyl (0.5), Butyl (3.0), Amyl (3.3), ≧Hex^(b) (6.0), ≧Am^(b) (10.0), ≧Bu^(b) (9.8) 88 6a(A) ^(d) ^(d) ^(d) ¹³C NMR: 6.4 Total Methyls; Branch Lengths: Methyl (5.5) 89 6a(C-1) 19,600  7580 2.58 ¹H NMR: 30.2 Total Methyls 90 6a(C-2) 12,700  3680 3.45 108 ¹³C NMR: 38.8 Total Methyls; Branch Lengths: Methyl (23.1), Ethyl (4.0), Propyl (1.8), Butyl (0), Amyl (0.9), ≧Hex^(b) (2.6), ≧Am^(b) (5.7), ≧Bu^(b) (9.6) 91 6a(E) 10800 2910 3.71 101 ¹H NMR: 42.8 Total Methyls 92 6a(F) 128000  9040 14.1 131 ¹H NMR: 3.1 Total Methyls 93 7a(B) 22300 6170 3.62 127 94 8a(A) ^(d) ^(d) ^(d) 130 95 8a(B)  8770 1600 5.47  80 ¹³C NMR: 68.0 Total Methyls; Branch Lengths: Methyl (41.1), Ethyl (8.8), Propyl (0.5), Butyl (2.6), Amyl (5.6), ≧Hex^(b) (9.9), ≧Am^(b) (14.7), ≧Bu^(b) (16.8) 96 9a(A) ^(d) ^(d) ^(d) 130 ¹³C NMR: 18.7 Total Methyls; Branch Lengths: Methyl (16.0) 97 9a(B) 60800  590 103 124 ¹³C NMR: 119.0 Total Methyls; Branch Lengths: Methyl (66.0), Ethyl (22.5), Propyl (5.0), Butyl (8.7), Amyl (7.5), ≧Hex^(b) (15.5), ≧Am^(b) (23.9), ≧Bu^(b) (28.4) 98 10a(A) 25600 6180 4.14 128 ¹H NMR: 11.4 Total Methyls 99 11a(B) 77500 3090 25.1 119 100  13a(B) 15500 3580 4.33  97 101  14a(A) ^(d) ^(d) ^(d) 129 102  14a(B) 68900 3070 22.4  78 103  15a(B) 23800 7560 3.15 129 ¹H NMR: 57.8 Total Methyls 104  16a(B) 69400  885 78.4 117 ¹³C NMR: 48 Total Methyls; Branch Lengths: Methyl (24.8), Ethyl (5.9), Propyl (1), Butyl (2.6), Amyl (6), ≧Hex^(b) (11.8), ≧Am^(b) (14.2), ≧Bu^(b) (16.3) 105  17a(A) ^(d) ^(d) ^(d) 132 ¹H NMR: 19.5 Total Methyls 106  17a(B) 325000  2080 156 128 ¹³C NMR: 25.2 Total Methyls; Branch Lengths: Methyl (17.9), Ethyl (4.3), Propyl (1.3), Butyl (1.9), Amyl (2.5), ≧Hex^(b) (3.7), ≧Am^(b) (4.4), ≧Bu^(b) (0.8) 107  18a(A) 24800 8730 2.84 ¹H NMR: 22.8 Total Methyls 108  19a(A) 90600 1630 55.7 123 ¹³C NMR: 47.4 Total Methyls; Branch Lengths: Methyl (23.7), Ethyl (5.6), Propyl (1.4), Butyl (2.1), Amyl (6.6), ≧Hex^(b) (12.7), ≧Am^(b) (14.8), ≧Bu^(b) (16.7) ^(a)Reaction conditions are given in Table 1. ^(b)Includes ends of chains. ^(c)Heterogeneous conditions in the glass insert during mixing can account for the observation of two Tm's. ^(d)GPC could not be performed due to the insolubility of the sample.

TABLE 4 Polyethylene Yields: Demonstration of Effects of Reaction Conditions and Reproducibility of Yields Using Rapid Screening Techniques with Compound 6 Polyethylene Yield (g) Run Run Run Run Run Ex. Reaction Conditions^(b) 1 2 3 4 5 109- A: 5 mL C₆D₆, rt, 18 h, ^(a) 0.10 0.10 ^(a) 1.3^(c) 113 6.9 MPa E, 2 equiv BPh₃ 114- B: 5 mL CDCl₃, 80° C., 18 h, 0.10 0.28 115 6.9 MPa E, 1 equiv B(C₆F₅)₃ 116- C: 5 mL C₆D₆, 80° C., 18 h, 9.50 9.55 0.49^(d) 118 6.9 MPa E, 2 equiv BPh₃ 119- G: 5 mL CDCl₃, rt, 18 h, ^(a) 0.65 7.78 121 6.9 MPa E, 2 equiv B(C₆F₅)₃ 122- H: 5 mL CDCl₃, 80° C., 18 h, 1.09 1.09 123 6.9 MPa E, 2 equiv B(C₆F₅)₃ ^(a)Less than 0.1 g of polyethylene was isolated. ^(b)E: Ethylene; H²(CO₂Me)CH₂ initiator was used unless otherwise noted. ^(c)1 equiv of BPh₃ was used. ^(d)H₂CCHCHCl allyl initiator was used.

TABLE 5 Polymerization of Ethylene and Propylene at Low Pressures Cmpd Polymer Ex. (mmol) Conds^(a) Gas (kPa)^(b) (g) TO^(c) T_(m) (° C.) 124 1a(0.11) I E(27-35) 2.91 970 ^(d) 125 6a(0.12) I E(27-35) 0.42 128 125  126 15a(0.15)  I E(27-35) 0.11  27 121^(e) 127 20a(0.11)  I E(27-35) 0.27  88 ^(f) 128 1a(0.06) J P(48) 1.84 730 ^(g) 129 1a(0.06) K P(48) 0.21  81 ^(h) 130 6a(0.06) L  P(600) 11.2^(i) 4400^(i ) j ^(a)Reaction conditions are defined in Table 1. ^(b)E: Ethylene. P: Propylene. ^(c)TO: number of turnovers per catalyst center = (moles monomer consumed, as determined by the weight of the isolated polymer or oligomers) divided by (moles catalyst). ^(d)Clear, rubbery amorphous PE. ^(e)White, rubbery PE. ^(f)White, crystalline PE. ^(g)Clear rubbery PP. ^(h)Clear sticky PP. ^(i)14 mL of liquid oligomers were isolated. A density of 0.8 g/mL was assumed. ^(j)GC analysis indicates that pentamers, hexamers and heptamers predominate.

EXAMPLES 131-136 Styrene and Norbornene Homo- and Copolymerizations

In the subsequent examples describing polymerizations of styrene and norbornene, all 5 manipulations were carried out in a nitrogen-purged drybox. Anhydrous solvents were used. The styrene (99+%, Aldrich, inhibited with 4-tert-butylcatechol) was degassed, filtered through basic alumina and inhibited with phenothiazine (98+%, Aldrich, 50 ppm) before use. The norbornene was purified by vacuum sublimation. Tacticities of polystyrenes were measured according to the following reference: T. Kawamura et al., Macromol. Rapid Commun. 1994, 15, 479-486.

General Procedure for Styrene Polymerizations. The nickel complex (0.03 mmol) was slurried in dry toluene (6 mL) and styrene (1.3 mL, 1.18 g, 11.3 mmol) was added. Two equiv of B(C₆F₅)₃ were then added with vigorous stirring. The resulting mixture was shaken at rt in the dark for 16 h after which time the sample was removed from the drybox and MeOH was added to precipitate the polymer. The solid polymer was isolated, redissolved in CHCl₃ and reprecipitated with MeOH to remove catalyst impurities. The product was then collected on a frit, washed with MeOH and finally with a MeOH/acetone/Irganox® 1010 solution.

General Procedure for Norbornene Polymerizations. The nickel complex (0.03 mmol) was slurried in dry toluene (6 mL) and norbornene (1.6 g, 17.0 mmol) was added. Two equiv of B(C₆F₅)₃ were then added with vigorous stirring. The resulting mixture was shaken at rt. After 16 h, the sample was removed from the drybox and MeOH was added to precipitate the polymer. The solid polymer was isolated. The polymer was redissolved or swollen with solvent in order to remove catalyst impurities and then reprecipitated with MeOH. The product was then collected on a frit, washed with MeOH and finally with an acetone/2% Irganox® 1010 solution.

General Procedure for Styrene/Norbornene Copolymerizations. The nickel complex (0.03 mmol) was slurried in dry toluene (5 mL) and a mixture of norbornene (1.17 g, 12.4 mmol) and styrene (1.4 mL, 1.27 g, 12.2 mmol) in toluene (3 mL) was added. Two equiv of B(C₆F₅)₃ were then added with vigorous stirring. The resulting mixture was shaken at rt in the dark for 5 h. The sample was then removed from the drybox and MeOH was added to precipitate the polymer. The isolated polymer was dissolved (CHCl₃) and reprecipitated (MeOH) to remove the catalyst residue. The product was stirred overnight in acetone to remove polystyrene and then filtered, washed with MeOH and finally with an acetone/2% Irganox® 1010 solution.

TABLE 6 Styrene (S) and Norbornene (N) Homo- and Copolymerizations Yield TO^(a) Ex. Cmpd Monomers (%) S N Mn^(b) PDI % S 131 3a S 79 300 — 2140 1.9 100^(c) 132 6a S 54 200 — 3390 1.8 100^(c) 133 3a N >95  — 570 ^(d) ^(d) Ñ 134 6a N >95  — 570 ^(d) ^(d) Ñ 135 3a S, N 21  13 170 9580 2.5   8 136 6a S, N  7  4  56 15500  2.0   7 ^(a)Number of turnovers: TO = (moles monomer consumed, as determined by the weight of the isolated polymer) divided by (moles catalyst). ^(b)M_(n) (GPC, TCB 120° C., polystyrene standards). ^(c13)C NMR spectroscopy (CDCl₃) indicates enrichment in meso diad units relative to atactic polystyrene. ^(d)Within 30 min the reaction mixture completely solidified and attempts to redissolve the polymer were unsuccessful. The insolubility of the polymer product indicates that an addition polymer of norbornene was formed.

Compounds 21-54. The syntheses and characterization of compounds 21-60 and their ligand precursors are reported in Examples 467 to 498. These compounds are used in the following Examples.

EXAMPLES 137-187 Styrene Homopolymerizations and Styrene/Norbornene Copolymerizations

In the subsequent examples describing polymerizations of styrene and norbornene, all manipulations were carried out in a nitrogen-purged drybox. Anhydrous solvents were used. The styrene (99+%, Aldrich, inhibited with 4-tert-butylcatechol) was degassed, filtered through basic alumina and inhibited with phenothiazine (98+%, Aldrich, 50 ppm) before use. The norbornene was purified by vacuum sublimation. Tacticities of polystyrenes were measured according to the following reference: T Kawamura et al., Macromol. Rapid Commun. 1994, 15, 479-486.

General Procedure for Styrene Polymerizations (Table 7). The nickel complex (0.03 mmol) was slurried in dry toluene (6 mL) and styrene (1.6 mL, 14 mmol) was added. Two equiv of B(C₆F₅)₃ were then added with vigorous stirring. The resulting mixture was shaken at rt in the dark for 5 h after which time the sample was removed from the drybox and MeOH was added to precipitate the polymer. The solid polymer was isolated, redissolved in CHCl₃ and reprecipitated with MeOH to remove catalyst impurities. The product was then collected on a frit, washed with MeOH and finally with a MeOH/acetone/Irganox® 1010 solution. The polymer was then dried under vacuum.

General Procedure for Styrene/Norbornene Copolymerizations (Table 8). The nickel complex (0.03 mmol) was slurried in dry toluene (5 mL) and a mixture of norbornene (1.41 g, 15 mmol) and styrene (1.7 mL, 15 mmol) in toluene (3 mL) was added. Two equiv of B(C₆F₅)₃ were then added with vigorous stirring. The resulting mixture was shaken at rt in the dark overnight. The sample was then removed from the drybox and added to MeOH to precipitate the polymer. The product was stirred overnight in acetone to remove polystyrene and then filtered, washed with MeOH and finally with an acetone/2% Irganox 1010 solution. The was then dried under vacuum.

TABLE 7 Styrene Homopolymerizations Yield Ex. Cmpd (%) TO^(a) M_(n) ^(b) PDI Tacticity 137  1a ^(e) ^(e) 138  2a ^(e) ^(e) 139  4a 41 192 16,000 2.0 enriched in meso diads^(c) 140  5a 61 282 14,900 2.1 enriched in meso diads^(c) 141  8a 15 70  2,390 3.8 enriched in meso diads^(c) 142  9a 0.7 3.2 143 14a 36 170  2,010 5.4 enriched in meso diads^(c) 144 15a 31 144  1,350 2.4 enriched in meso diads^(c) 145 16a ^(e) ^(e) 146 17a 9 42  5,800 2.2 enriched in meso diads^(c) 147 21a 72 336   770 2.7 enriched in meso diads^(c) 148 22a 66 304   760 2.7 enriched in meso diads^(c) 149 24a 73 340  1,010 2.9 enriched in meso diads^(c) 150 28a 48 221   730 2.9 enriched in meso diads^(c) 151 31a 57 265  2,230 1.8 enriched in meso diads^(c) 152 32a 78 362 14,900 2.1 enriched in meso diads^(c) 153 33a 26 122   830 2.3 enriched in meso diads^(c) 154 35a 6 29 18,800 5.1 highly isotactic 155  35a^(d) 29 134  4,150 6.8 highly isotactic 156 39a 4.1 19 enriched in r diads^(c) 157 40a 58 269   785 3.5 enriched in meso diads^(c) 158 42a 57 265   800 2.8 enriched in meso diads^(c) 159 46a 6 29  1,980 1.4 highly isotactic 160 47b 15 70  1,200 6.3 enriched in meso diads^(c) 161 48a 48 221  1,660 8.3 enriched in meso diads^(c) 162 49a 9 42 12,200 2.6 enriched in meso diads^(c) ^(a)Number of turnovers: TO = (moles styrene consumed, as determined by the weight of the isolated polymer) divided by (moles catalyst). ^(b)M_(n) (GPC, TCB, 120° C., polystyrene standards). ^(c)According to ¹³C NMR spectroscopy (CDCl₃) and relative to atactic polystyrene. ^(d)60° C. ^(e)No polymer was isolated.

TABLE 8 Styrene (S) and Norbornene (N) Copolymerizations TO^(a) Ex. Cmpd Yield (%) S N M_(n) ^(b) PDI % S 163  1a 4.7 ^(c)  47 5,330 5 <5 164  2a 40 ^(c) 400 11,000  3.9 <5 165  4a 43 44 390 7,630 3.3 11 166  5a 27 15 251 5,430 2.3 6.7 167  8a 14 ^(c) 141 14,300  2.7 <5 168  9a 8.5 ^(c)  84 8,100 2.3 <5 169 14a 32 17 303 7,290 3.4 5.8 170 15a 36 29 329 7,140 3.0 9 171 16a 8.8 ^(c)  92 6,920 2.6 <5 172 17a 7.8 ^(c)  78 7,060 2.3 <5 173 21a 44 41 400 2,730 3.8 10.2 174 22a 47 45 425 3,340 3.3 10.5 175 24a 15  5 142 5,800 3.0 3.7 176 28a 45 47 415 2,680 3.9 11.2 177 31a 30 ^(c) 300 4,700 2.4 <5 178 32a 26 19 236 5,670 2.2 7.5 179 33a 31 13 300 5,940 2.6 4.5 180 35a 7.4 ^(c)  74 20,500  2.4 <5 181 39a 3.0 ^(c) 262 5,054 2.9 <5 182 40a 18  5 172 5,960 2.9 3.0 183 42a 43 31 398 2,470 4.4 8.7 184 46a 38 ^(c) 379 14,800  2.8 <5 185 47b 17 ^(c) 170 4,570 6.2 <5 186 48a 8 ^(c)  78 17,600  2.5 <5 187 49a 15 ^(c) 145 7,500 2.3 <5 ^(a)Number of turnovers: TO = (moles monomer consumed, as determined by the weight of the isolated polymer) divided by (moles catalyst). ^(b)M_(n) (GPC, TCB, 120° C., polystyrene standards). ^(c)Low styrene incorporation (<5%) precluded calculation of the styrene turnover numbers.

EXAMPLES 188-194 Norbornene Homopolymerizations and Norbornene/Functionalized-Norbornene Copolymerizations EXAMPLE 188 Norbornene Homopolymerization Catalyzed by 52/B(C₆F₅)₃

In a 20 mL scintillation vial under nitrogen, compound 52 (0.010 g, 0.021 mmol) and norbornene (1.00 g, 10.62 mmol) were dissolved in 5 mL of toluene to give an orange solution. To this was added B(CEF₅)₃ (0.011 g, 0.022 mmol). After 30 min at ambient temperature, more B(C₆F₅)₃ was added to the reaction mixture (0.110 g, 0.214 mmol). An extremely viscous, yellow suspension formed very rapidly and within minutes the reaction mixture could no longer be stirred. Twenty-three h after the initial addition of B(C₆F₅)₃, the reaction mixture was quenched by addition of methanol under air. Further workup afforded 0.93 g of polymer. ¹H NMR (1,1,2,2-tetrachloroethane-d₂, 120° C.) indicated that the polymer was the addition polymer of norbornene formed without double bond ring-opening.

EXAMPLE 189 Copolymerization of Norbornene With the Dimethyl Ester of Endo-5-norbornene-2,3-Dicarboxylic Acid Catalyzed by 21a/B(C₆F₅)₃ (Copolymer: ˜30 Mole % Dimethyl Ester)

In a 20 mL scintillation vial under nitrogen, compound 21a (0.015 g, 0.029 mmol), norbornene (0.500 g, 5.31 mmol), and the dimethyl ester of 5-norbornene-2,3-dicarboxylic acid (1.00 g, 4.76 mmol) were dissolved in 10 mL of toluene. To this solution was added solid B(C₆F₅)₃ (0.029 g, 0.058 mmol). The resulting solution was stirred initially at ambient temperature by means of a magnetic stirbar; however, after several minutes the reaction mixture consisted of a viscous, solvent-swollen polymer that could not be stirred. Twenty-seven h after the addition of B(C₆F₅)₃, the reaction mixture was quenched by addition of the solvent-swollen reaction mixture to methanol under air. The precipitated polymer was filtered off, washed with methanol, and dried to afford 0.810 g of addition copolymer. ¹H NMR (CD₂Cl₂, 25° C.) indicated the following composition: norbornene (74 mole %), dimethyl ester (26 mole %). Quantitative ¹³C NMR (tr4chlorobenzene-d₃, 100° C.) indicated the following composition: norbornene (70.8 mole %), dimethyl ester (29.2 mole %).

EXAMPLE 190 Copolymerization of Norbornene With the Dimethyl Ester of Endo-5-norbornene-2,3-Dicarboxylic Acid Catalyzed by 21a/B(C₆F₅)₃ (Copolymer: 22 Mole % Dimethyl Ester)

A reaction identical to that above in Example 189, but run in CH₂Cl₂ instead of toluene gave the following results: Yield=0.63 g. ¹H NMR (CDCl₃, 25° C.) indicated the following composition: norbornene (81%), dimethyl ester (19%). Quantitative ¹³C NMR (trichlorobenzene-d₃, 100° C.): norbornene (78.11 mole %), dimethyl ester (21.89 mole %).

EXAMPLE 191 Copolymerization of Norbornene with the Dimethyl Ester of Endo-5-norbornene-2,3-Dicarboxylic Acid Catalyzed by 21a/B(C₆F₅)₃ (Copolymer: ˜11 mole % Dimethyl Ester)

In a 20 mL scintillation vial under nitrogen, compound 21a (0.015 g, 0.029 mmol), norbornene (3.00 g, 31.86 mmol), the dimethyl ester of 5-norbornene-2,3-dicarboxylic acid (1.00 g, 4.76 mmol), and B(C₆F₅)₃ (0.029 g, 0.058 mmol) were dissolved in 10 mL of toluene. The resulting yellow solution was stirred initially at ambient temperature by means of a magnetic stirbar; however, within 15 minutes an extremely rapid, highly exothermic reaction ensued. The reaction mixture setup and could not be stirred after this point. Three h after the addition of B(C₆F₅)₃, the reaction mixture was quenched by addition of the solvent-swollen reaction mixture to methanol under air. Further workup afforded 3.75 g of addition copolymer. ¹H NMR (CDCl₃, 25° C.) indicated the following composition: norbornene (90 mole %), dimethyl ester (10 mole %). Quantitative 13C NMR (trichlorobenzene-d₃, 100° C.) indicated the following composition: norbornene (89.05 mole %), dimethyl ester (10.95 mole %).

EXAMPLE 192 Copolymerization of Norbornene With the Dimethyl Ester of Endo-5-norbornene-2,3-Dicarboxylic Acid Catalyzed by 21a/B(C₆F₅)₃ (Copolymer: 6 mole % Dimethyl Ester)

A reaction identical to that above in Example 191, but run in CH₂Cl₂ instead of toluene gave the following results: Yield=3.12 g. ¹H NMR (CDCl₃, 25° C.) indicated the following composition: norbornene (96 mole %), dimethyl ester (4 mole %). Quantitative ¹³C NMR (trichlorobenzene-d₃, 100° C.): norbornene (94.19 mole %), dimethyl ester (5.81 mole %).

EXAMPLE 193 Copolymerization of Norbornene With the t-Bu Ester of 5-Norbornene-2-Carboxylic Acid Catalyzed by 50/B(C₆F₅)₃ (Copolymer: ˜30 mole % t-Bu Ester)

In a 20 mL scintillation vial under nitrogen, compound 50 (0.010 g, 0.020 mmol), norbornene (0.500 g, 5.31 mmol), and the t-Bu ester of 5-norbornene-2-carboxylic acid (1.00 g, 5.15 mmol) were dissolved in 5 mL toluene. To this solution was added B(C₆F₅)₃ (0.102 g, 0.200 mmol). The resulting yellow solution was stirred at ambient temperature for 16 h. The reaction mixture was quenched and the copolymer precipitated by addition of methanol under air. Further workup afforded 0.664 g of addition copolymer. Quantitative ¹³C NMR (trichlorobenzene-d₃, 100° C.) indicated the following composition: norbornene (70.4 mole %), t-Bu ester (29.6 mole %).

EXAMPLE 194 Copolymerization of Norbornene With the Dimethyl Ester of Endo-5-norbornene-2,3-Dicarboxylic Acid Catalyzed by 52/B(C₆F₅)₃ (Copolymer: ˜32 mole % Dimethyl Ester)

In a 20 mL scintillation vial under nitrogen, compound 52 (0.010 g, 0.021 mmol), norbornene (0.500 g, 5.31 mmol), and the dimethyl ester of 5-norbornene-2,3-dicarboxylic acid (1.00 g, 4.76 mmol) were dissolved in 5 mL of toluene. To this solution was added a suspension of B(C₆F₅)₃ (0.029 g, 0.058 mmol) in 5 mL of toluene. The resulting orange solution was stirred initially at ambient temperature by means of a magnetic stirbar; however, after several minutes the reaction mixture consisted of a viscous, solvent-swollen polymer that could not be stirred. Twenty-two h after the addition of B(C₆F₅)₃, the reaction mixture was quenched by addition of the solvent-swollen reaction mixture to methanol under air. The precipitated polymer was filtered off, washed with methanol, and dried to afford 0.930 g of addition copolymer. ¹H NMR (CDCl₃, 25° C.) indicated the following composition: norbornene (68 mole %), dimethyl ester (32 mole %).

EXAMPLES 195-366 Ethylene Polymerizations

General Procedure for Ethylene Polymerizations of Table 9

Pressure Tube Loaded Outside of the Drybox Under a Nitrogen Purge

(In the ethylene polymerization reactions of Tables 2, 3, and 4, the glass inserts were also loaded in the pressure reactor tube outside of the drybox under a nitrogen purge.) Procedure. In the drybox, a glass insert was loaded with the isolated allyl initiator (0.06 mmol). The insert was cooled to −35° C. in the drybox freezer, 5 mL of C₆D₆ was added to the cold insert, and the insert was cooled again. A Lewis acid cocatalyst [typically BPh₃ or B(C₆F₅)₃] was added to the cold solution, and the insert was then capped and sealed. Outside of the drybox, the cold insert was placed under a nitrogen purge into the pressure tube. The pressure tube was sealed, placed under ethylene (6.9 MPa), and allowed to warm to rt as it was shaken mechanically for approximately 18 h. An aliquot of the solution was used to acquire a ¹H NMR spectrum. The remaining portion was added to ˜20 mL of MeOH in order to precipitate the polymer. The polyethylene was isolated and dried under vacuum.

General Procedure for Ethylene Polymerizations of Tables 10-14

Pressure Tube Loaded and Sealed in the Drybox Under a Nitrogen Atmosphere

Procedure. In the drybox, a glass insert was loaded with the nickel compound. Often, a Lewis acid (typically BPh₃ or B(C₆F₅)₃) was also added to the glass insert. Next, 5 mL of a solvent (typically 1,2,4-trichlorobenzene although p-xylene, cyclohexane, etc. were also used at times) was added to the glass insert and the insert was capped. The glass insert was then loaded in the pressure tube inside the drybox. The pressure tube containing the glass insert was then sealed inside of the drybox, brought outside of the drybox, connected to the pressure reactor, placed under the desired ethylene pressure and shaken mechanically. After the stated reaction time, the ethylene pressure was released and the glass insert was removed from the pressure tube. The polymer was precipitated by the addition of MeOH (˜20 mL) and concentrated HCl (˜1-3 mL). The polymer was then collected on a frit and rinsed with HCl, MeOH, and acetone. The polymer was transferred to a pre-weighed vial and dried under vacuum overnight. The polymer yield and characterization were then obtained.

TABLE 9 Ethylene Polymerization (6.9 MPa, C₆D₆ (5 mL), 0.06 mmol Cmpd, 18 h) Temp Lewis M.W.^(c) (MI, GPC, Total Ex. Cmpd (° C.) Acid^(a) PE(g) PE(TO)^(b) and/or ¹H NMR) Me^(d) 195 21a 25 BPh₃ 3.34 2,000 MI: 79.5; M_(n)(¹H): 3,670 36.9 196 21a 80 B(C₆F₅)₃ ^(e) ^(e) 197 22a 25 BPh₃ 4.41 2,600 MI > 200; M_(n)(¹H): 1,890 85.5 198 22a 80 B(C₆F₅)₃ 0.04   20 199 24a 25 BPh₃ 15.3 9,100 MI < 0.01; M_(n)(¹H): no olefins 4.5 200 24a 80 B(C₆F₅)₃ 0.15   91 201 28a 25 BPh₃ 0.30   180 M_(n)(¹H): 18,900 67.1 202 28a 80 B(C₆F₅)₃ 0.04   24 203 31a 25 BPh₃ ^(f) ^(f) 204 31a 80 B(C₆F₅)₃ ^(f) ^(f) 205 32a 25 BPh₃ 0.01^(e)     7^(e) 206 32a 80 B(C₆F₅)₃ ^(e) ^(e) 207 33a 25 BPh₃ 0.21   120 208 33a 80 B(C₆F₅)₃ 1.60   950 MI: 79.5; M_(n)(¹H): 1,390 51.2 209 35a 25 BPh₃ 0.19^(e)    110^(e) 210 35a 80 B(C₆F₅)₃ 0.11^(e)    68^(e) 211 37a 25 BPh₃ 0.02^(e)    10^(e) 212 38a 80 B(C₆F₅)₃ 0.07^(e)    42^(e) 213 39a 25 BPh₃ ^(f) ^(f) 214 39a 80 B(C₆F₅)₃ 2.11 1,300 MI: 105; M_(n)(¹H): 5,200 21.5 215 40a 25 BPh₃ 0.08^(e)    50^(e) 216 40a 80 B(C₆F₅)₃ ^(e) ^(e) 217 42a 25 BPh₃ ^(e) ^(e) 218 42a 80 B(C₆F₅)₃ ^(e) ^(e) 219 46a 25 BPh₃ ^(f) ^(f) 220 46a SO B(C₆F₅)₃ 0.11   65 221 47b 25 BPh₃ 0.12^(e)    71^(e) 222 47b 80 B(C₆F₅)₃ ^(e) ^(e) 223 47b 25 BPh₃ 0.15   91 224 47b 80 B(C₆F₅)₃ 0.09   52 225 48a 25 BPh₃ 0.07   43 226 48a 80 B(C₆F₅)₃ 0.22    132^(e) 227 49a 25 BPh₃ 0.10   59 228 49a 80 B(C₆F₅)₃ 0.06^(e)    34^(e) ^(a)Two equiv. ^(b)TO: number of turnovers per metal center = (moles ethylene consumed, as determined by the weight of the isolated polymer or oligomers) divided by (moles catalyst). ^(c)M.W.: Molecular weight of the polymer or oligomers as determined by melt index (MI: g/10 min at 190° C.), GPC (molecular weights are reported versus polystyrene standards; conditions: Waters 150C, trichlorobenzene at 150° C., Shodex columns at −806MS 4G 734/602005, RI detector), and/or ¹H NMR (olefin end group analysis). ^(d)Total number of methyl groups per 1000 methylene groups determined by ¹H NMR analysis. ^(e1)H NMR: oligomers and/or (CH₂)_(n) peak observed. ^(f)PE was not obtained in isolable quantities. ^(g)The general procedure for the screening of ethylene polymerizations by nickel allyl initiators at 6.9 MPa ethylene (see above) was followed.

TABLE 10 Ethylene Polymerizations at 6.9 MPa: Pressure Tube Loaded in the Drybox under N₂ Atmosphere (Trichlorobenzene (5 mL), 18 h) Temp Lewis M.W.^(c) (MI, GPC, Total Ex. Cmpd^(f) (° C.) Acid^(a) PE(g) PE(TO)^(b) and/or ¹H NMR) Me^(d) 229  3a 25 BPh₃ 8.31 12,900  MI: 5.5; M_(n)(¹H): 18,100 36.9 230   3a^(g) 25 BPh₃ 1.54 3,660 MI: 40; M_(n)(¹H): no olefins 20.0 231   3a^(g) 25 B(C₆F₅)₃ 0.701 1,460 MI: 22.9; M_(n)(¹H): 99,900 22.9 232  3a 80 BPh₃ 4.29 6,640 MI > 200; M_(n)(¹H): 4,770 56.2 233  3a 80 B(C₆F₅)₃ 0.203   359 Mn(¹H): 2,500 47.7 234  4a 25 BPh₃ 2.44 4,630 MI: 126; M_(n)(¹H): 10,300 43.5 235  4a 80 BPh₃ 2.19 3,640 MI > 200; M_(n)(¹H): 2,270 75.5 236  4a 80 B(C₆F₅)₃ 0.096   190 Mn(¹H): 3,260 29.3 237  5a 25 BPh₃ 4.98 8,630 M_(w)(GPC): 14,100; PDI: 6.7 93.2 238  5a 80 BPh₃ 2.72 4,710 M_(n)(GPC): 2,850; PDI: 3.7 137.3 239  6a 25 BPh₃ 4.44 7,730 MI: 0.85 240   6a^(i) 25 B(C₆F₅)₃ 6.18 5,490 MI: 1.2; M_(n)(¹H): 9,620 28.5 241   6a^(g) 80 BPh₃ 4.13 10,500  MI: 21; M_(n)(¹H): 12,200 28.4 242   6a^(h) 80 BPh₃ 13.1 7,800 MI > 200; M_(n)(¹H): 3,030 79.0 243  6a 80 B(C₆F₅)₃ 3.31 5,990 MI: 81; M_(n)(¹H): 5,920 34.7 244   6a^(g) 80 B(C₆F₅)₃ 3.14 7,300 MI: 45 245   6a^(h) 80 B(C₆F₅)₃ 8.92 5,300 MI > 200; M_(n)(¹H): 1,420 89.1 246  7a 25 BPh₃ 0.93 1,350 MI < 0.01; M_(n)(¹H): no olefins 2.1 247  7a 25 B(C₆F₅)₃ 2.19 3,790 M_(n)(¹H): 4,160 11.6 248  7a 80 B(C₆F₅)₃ 1.36 2,030 MI: 35; M_(n)(¹H): 1,370 35.7 249  8a 25 BPh₃ 3.88 6,400 MI: 120; M_(n)(¹H): 2,990 57.2 250  8a 25 B(C₆F₅)₃ 6.95 11,800  MI: 2.6; M_(n)(¹H): 6,770 57.5 251  8a 80 B(C₆F₅)₃ 3.99 7,220 MI: 132 252  9a 25 BPh₃ 6.35 11,200  MI > 200; M_(n)(¹H): 4,910 64.9 253  9a 25 B(C₆F₅)₃ 6.32 9,900 MI: 102; M_(n)(¹H): 5,380 91.3 254  9a 80 B(C₆F₅)₃ 4.8 8,000 M_(n)(¹H): 1,410 134.6 255 10a 25 BPh₃ 0.18   320 256 10a 80 BPh₃ 1.33 2,140 MI: 63; M_(n)(¹H): 11,100 38.3 257 10a 80 B(C₆F₅)₃ 0.097   170 M_(n)(¹H): 2,010 30.4 258 11a 25 BPh₃ 0.11   190 259 11a 80 BPh₃ 1.33 2,140 MI: 160; M_(n)(¹H): 7,990 40.5 260 12a 25 BPh₃ 3.68 6,040 MI < 0.01 261 12a 80 BPh₃ 4.22 7,260 MI: 74; M_(n)(¹H): 9,260 33.0 262 12a 80 B(C₆F₅)₃ 1.61 2,870 MI: 30; M_(n)(¹H): 12,700 19.3 263 13a 25 BPh₃ 0.99 1,690 MI: 0.04; M_(n)(¹H): 23,400 20.5 264 13a 80 BPh₃ 3.73 6,580 MI: 147; M_(n)(¹H): 4,890 40.2 265 13a 80 B(C₆F₅)₃ 0.93 1,560 MI > 200; M_(n)(¹H): 4,520 36.5 266 14a 25 BPh₃ 1.68 3,120 MI: 0.3; M_(n)(¹H): 18,300 24.2 267 14a 25 B(C₆F₅)₃ 4.28 7,010 MI: 6; M_(n)(¹H): 5,820 42.6 268 14a 80 B(C₆F₅)₃ 1.52 2,760 MI: 117; M_(n)(¹H): 3,080 54.0 269 15a 25 BPh₃ 0.265   468 270 15a 25 BPh₃ 1.75 3,060 MI: 0.1; M_(n)(¹H): 1,900 30.7 271 15a 80 B(C₆F₅)₃ 0.399   705 M_(n)(¹H): 1,700 43.7 272 17a 25 BPh₃ 0.191   346 M_(n)(¹H): 23,500 273 17a 25 B(C₆F₅)₃ 5.69 10,100  MI < 0.01; M_(n)(¹H): 24,600 10.4 274 17a 80 B(C₆F₅)₃ 1.59 2,540 MI: 0.08; M_(n)(¹H): 7,130 24.1 275 18a 25 BPh₃ ^(e) ^(e) 276 18a 80 B(C₆F₅)₃ 0.046   76 M_(n)(¹H): 4,690 27.4 277 19a 25 BPh₃ 0.289   544 M_(n)(¹H): 4,450 36.2 278 19a 25 B(C₆F₅)₃ 0.223   399 M_(n)(¹H): 1,660 27.8 279 19a 80 BPh₃ 0.077   128 M_(n)(¹H): 2,550 39.3 280 19a 80 B(C₆F₅)₃ 0.224   399 M_(n)(¹H): 839 52.5 281 21a 25 BPh₃ 6.48 10,700  MI: 42; M_(n)(¹H): 21,400 24.9 282 21a 80 BPh₃ 3.44 6,090 MI > 200; M_(n)(¹H): 4,010 52.5 283 21a 80 B(C₆F₅)₃ 0.123   226 284 21b 25 BPh₃ 4.15 6,060 MI: 16.5; M_(n)(¹H): 21,600 19.9 285 21b 25 B(C₆F₅)₃ 0.024   31 M_(n)(¹H): 1,570 34.2 286 21b 80 BPh₃ 3.39 5,640 MI > 200; M_(n)(¹H): 3,730 55.2 287 21b 80 B(C₆F₅)₃ 0.030   48 M_(n)(¹H): 2,190 38.7 288 22a 25 BPh₃ 10.1 17,900 MI > 200; M_(n)(¹H): 2,600 85.1 289 22a 80 BPh₃ 4.11 7,120 Mn(¹H): 1,630 92.6 290 22a 80 B(C₆F₅)₃ 0.15   260 Mn(¹H): no olefins 23.7 291 23a 25 BPh₃ 2.93 4,770 MI > 200; M_(n)(¹H): 7,220 59.1 292 23a 25 BPh₃ 2.90 4,960 MI: 120; M_(n)(¹H): 8,950 56.5 293 23a 80 B(C₆F₅)₃ ^(e) ^(e) 294 24a 25 BPh₃ 1.73 3,250 MI< 0.01; M_(n)(¹H): no olefins 8.6 295 24a 80 BPh₃ 1.95 3,340 MI: 29; M_(n)(¹H): 8,110 28.6 296 24a 80 B(C₆F₅)₃ 1.16 2,060 MI: 70; M_(n)(¹H): 8,540 23.0 297 25a 25 BPh₃ 9.07 17,000  MI: 1.4 298 25a 80 BPh₃ 3.64 6,450 MI > 200; M_(n)(¹H): 3,310 54.2 299 25a 80 B(C₆F₅)₃ 0.025   47 M_(n)(¹H): 3,140 31.6 300 26a 25 BPh₃ 7.89 13,700 MI > 200; M_(n)(¹H): 3,250 69.2 301 26a 25 BPh₃ 11.7 17,900 MI > 200; M_(n)(¹H): 3,930 66.6 302 26a 80 B(C₆F₅)₃ ^(e) ^(e) 303 27a 25 BPh₃ 4.47 7,800 MI: 210; M_(n)(¹H): 8,040 52.7 304 27a 25 BPh₃ 7.03 11,500  MI: 108; M_(n)(¹H): 8,230 50.9 305 27a 80 B(C₆F₅)₃ 0.009   17 M_(n)(¹H): 5,070 27.9 306 28a 25 BPh₃ 0.761 1,300 MI: 60; M_(n)(¹H): 19,900 37.1 307 28a 25 BPh₃ 0.271   481 M_(n)(¹H): 26,700 31.3 308 28a 80 B(C₆F₅)₃ 0.006   10 M_(n)(¹H): 6,630 19.8 309 29a 25 B(C₆F₅)₃ 0.573   994 MI: 0.12; M_(n)(¹H): 4,010 16.2 310 29a 25 BPh₃ ^(e) ^(e) 311 29a 80 B(C₆F₅)₃ 0.199   360 M_(n)(¹H): 1,650 35.3 312 30a 25 B(C₆F₅)₃ 2.45 4,160 MI < 0.01; M_(n)(¹H): 8,300 8.1 313 30a 25 BPh₃ ^(e) ^(e) 314 30a 80 B(C₆F₅)₃ 1.64 2,610 MI: 17; M_(n)(¹H): 3,600 23.0 315 33a 25 BPh₃ 0.431   768 M_(n)(¹H): 21,300 3.4 316 33a 25 B(C₆F₅)₃ 2.35 4,070 MI: 0.13; M_(n)(¹H): 4,270 37.1 317 33a 80 B(C₆F₅)₃ 0.915 1,540 MI: 36.8: M_(n)(¹H): 1,860 36.1 318 34a 25 B(C₆F₅)₃ 7.53 11,600  Mn(¹H): 3,450 72.4 319 34a 80 B(C₆F₅)₃ 5.35 7,570 M_(w)(GPC): 29,100; PDI: 46 113.2 320 36a 25 BPh₃ 9.31 15,300  M_(n)(GPC): 461,000; PDI: 3.3 8.0 321 36a 80 BPh₃ 0.353   564 M_(n)(GPC): 30,000; PDI: 4.0 25.8 322 37a 25 BPh₃ 0.919 1,650 MI: 0.06; M_(n)(¹H): no olefins 14.4 323 37a 25 BPh₃ 0.299   434 M_(n)(¹H): 31,100 15.0 324 37a 80 B(C₆F₅)₃ 0.269   434 M_(n)(¹H): 5,200 40.4 325 38a 25 BPh₃ 1.43 2,470 MI: 111; M_(n)(¹H): 6,150 65.8 326 38a 80 BPh₃ 1.55 2,580 MI > 200; M_(n)(¹H): 2,780 99.2 327 39a 25 B(C₆F₅)₃ 0.414   814 M_(n)(¹H): 10,700 7.7 328 39a 25 BPh₃ ^(e) ^(e) 329 39a 25 BPh₃ ^(e) ^(e) 330 39a 80 B(C₆F₅)₃ 0.758 1,290 MI: 80; M_(n)(¹H): 5,190 20.1 331 41a 25 BPh₃ 0.316   586 M_(n)(¹H): no olefins 11.5 332 41a 25 B(C₆F₅)₃ 4.08 6,690 MI < 0.01; Mn(¹H): 30,700 30.9 333 41a 80 B(C₆F₅)₃ 2.26 3,730 MI: 180; M_(n)(¹H): 9,960 36.9 334 43a 25 BPh₃ ^(e) ^(e) 335 43a 25 B(C₆F₅)₃ 0.53   918 M_(n)(¹H): 3,600 36.6 336 43a 80 BPh₃ ^(e) ^(e) 337 43a 80 B(C₆F₅)₃ 0.054   93 M_(n)(¹H): 2,960 32.0 338 44a 25 B(C₆F₅)₃ 0.167   291 M_(n)(GPC): 136,000; PDI: 18 25.4 339 44a 80 B(C₆F₅)₃ 0.019   34 Mn(¹H): 5,150 43.3 340 45a 25 B(C₆F₅)₃ 0.026   43 M_(n)(¹H): 5,150 8.6 341 45a 80 B(C₆F₅)₃ trace trace M_(n)(¹H): 6,310 14.2 ^(a)Two equiv. ^(b)TO: number of turnovers per metal center = (moles ethylene consumed, as determined by the weight of the isolated polymer or oligomers) divided by (moles catalyst). Calculations are based upon the exact amount of catalyst used. ^(c)M.W.: Molecular weight of the polymer or oligomers as determined by melt index (MI: g/10 min at 190° C.), GPC (molecular weights are reported versus polystyrene standards; conditions: Waters 150C, trichlorobenzene at 150° C., Shodex columns at −806MS 4G 734/602005, RI detector), and/or ¹H NMR (olefin end group analysis). ^(d)Total number of methyl groups per 1000 methylene groups as determined by ¹H NMR analysis. ^(e)PE was not obtained in isolable quantities. ^(f)0.02 mmol unless noted otherwise. ^(g)0.015 mmol. ^(h)0.06 mmol. ^(i)0.04 mmol.

TABLE 11 Ethylene Polymerizations at 6.9 MPa Pressure Tube Loaded in the Drybox under N₂ Atmosphere (p-Xylene, (5 mL), 18 h) Temp Lewis M.W.^(c) (MI, GPC, Total Ex. Cmpd^(f) (° C.) Acid^(a) PE(g) PE(TO)^(b) and/or ¹H NMR) Me^(d) 342 3a^(h) 25 BPh₃ 20.2 12,000  MI: 2.6 343 3a^(g) 25 BPh₃ 0.19   366 344 3a^(g) 25 B(C₆F₅)₃ 0.48 1,160 M_(n)(¹H): 27,100 24.4 345 6a^(h) 80 BPh₃ 11.1 6,610 MI: 105; M_(n)(¹H): 9,090 31.1 346 6a^(h) 80 B(C₆F₅)₃ 6.90 4,100 MI: > 200; M_(n)(¹H): 3,170 63.4 347 6a^(g) 80 B(C₆F₅)₃ 3.47 8,470 MI: 58.8; M_(n)(¹H): 6,880 34.5 ^(a)Two equiv. ^(b)TO: number of turnovers per metal center = (moles ethylene consumed, as determined by the weight of the isolated polymer or oligomers) divided by (moles catalyst). Calculations are based upon the exact amount of catalyst used. ^(c)M.W.: Molecular weight of the polymer or oligomers as determined by melt index (MI: g/10 min at 190° C.), GPC (molecular weights are reported versus polystyrene standards; conditions: Waters 150C, trichlorobenzene at 150° C., Shodex columns at −806MS 4G 734/602005, RI detector), and/or ¹H NMR (olefin group analysis). ^(d)Total number of methyl groups per 1000 methylene groups as determined by ¹H NMR analysis. ^(e)PE was not obtained in isolable quantities. ^(f)0.02 mmol unless noted otherwise. ^(g)0.015 mmol. ^(h)0.06 mmol.

TABLE 12 Ethylene Polymerizations at 6.9 MPa Pressure Tube Loaded in the Drybox under N₂ Atmosphere (Cyclohexane, (5 mL), 18 h) Temp Lewis M.W.^(c) (MI, GPC, Total Ex. Cmpd^(f) (° C.) Acid^(a) PE(g) PE(TO)^(b) and/or ¹H NMR) Me^(d) 348 3a^(g) 25 BPh₃ 0.52 1,160 349 6a^(h) 80 BPh₃ 10.6 6,270 MI: 135; M_(n)(¹H): 7,410 33.8 350 6a^(g) 80 BPh₃ 7.07 16,810  MI: 129; M_(n)(¹H): 8,800 27.7 ^(a)Two equiv. ^(b)TO: number of turnovers per metal center = (moles ethylene consumed, as determined by the weight of the isolated polymer or oligomers) divided by (moles catalyst). Calculations are based upon the exact amount of catalyst used. ^(c)M.W.: Molecular weight of the polymer or oligomers as determined by melt index (MI: g/10 min at 190° C.), GPC (molecular weights are reported versus polystyrene standards; conditions: Waters 150C, trichlorobenzene at 150° C., Shodex columns at −806MS 4G 734/602005, RI detector), and/or ¹H NMR (olefin end group analysis). ^(d)Total number of methyl groups per 1000 methylene groups as determined by ¹H NMR analysis. ^(e)PE was not obtained in isolable quantities. ^(f)0.02 mmol unless noted otherwise. ^(g)0.015 mmol. ^(h)0.06 mmol.

TABLE 13 Ethylene Polymerizations at 1.4 MPa Pressure Tube Loaded in the Drybox under N₂ Atmosphere (Trichlorobenzene (5 mL) 0.02 mmol Cmpd, 18 h) Temp Lewis M.W.^(c) (MI, GPC, Total Ex. Cmpd (° C.) Acid^(a) PE(g) PE(TO)^(b) and/or ¹H NMR) Me^(d) 351  3a 25 BPh₃ 1.71 2,540 MI: 0.26; M_(n)(¹H): 64,600 17.3 352  4a 25 BPh₃ 2.87 5,000 MI: 92; M_(n)(¹H): 15,300 40.3 353  6a 25 B(C₆F₅)₃ 2.31 3,760 MI: 1; M_(n)(¹H): 11,700 55.0 354  8a 25 B(C₆F₅)₃ 2.10 3,440 MI: 123; M_(n)(¹H): 5,570 81.5 355  9a 25 B(C₆F₅)₃ 1.53 2,730 M_(n)(¹H): 4,850 112.3 356 14a 25 B(C₆F₅)₃ 1.18 2,080 MI: 7.5; M_(n)(¹H): 4,730 53.3 357 21a 25 BPh₃ 1.58 2,670 MI: 1.5; M_(n)(¹H): 14,700 39.9 358 22a 25 BPh₃ 2.94  4740 MI > 200; M_(n)(¹H): 4,580 73.7 359 25a 25 BPh₃ 1.18 2,060 MI: 6.6; M_(n)(¹H): 5,020 110.6 360 26a 25 BPh₃ 2.41 4,040 MI > 200; M_(n)(¹H): 3,870 73.6 ^(a)Two equiv. ^(b)TO: number of turnovers per metal center = (moles ethylene consumed, as determined by the weight of the isolated polymer or oligomers) divided by (moles catalyst). Calculations are based upon the exact amount of catalyst used. ^(c)M.W.: Molecular weight of the polymer or oligomers as determined by melt index (MI: g/10 min at 190° C.), GPC (molecular weights are reported versus polystyrene standards; conditions: Waters 150C, trichlorobenzene at 150° C., Shodex columns at −806MS 4G 734/602005, RI detector), and/or ¹H NMR (olefin end group analysis). ^(d)Total number of methyl groups per 1000 methylene groups as determined ¹H NMR analysis. ^(e)PE was not obtained in isolable quantities.

TABLE 14 Ethylene Polymerizations Using Nickel Methyl Initiators: Effect of Lewis Acid on Initiation/Productivity (6.9 MPa, 0.02 mmol Cmpd. Trichlorobenzene (5 mL), 18 h) Temp Lewis M.W.^(b) (MI, GPC, Total Ex. Cmpd (° C.) Acid (equiv) PE(g) PE(TO)^(a) and/or ¹H NMR) Me^(c) 361  50^(d) 25 none trace trace 362  50^(d) 80 none 0.189   307 M_(n)(¹H): 5,840 39.4 363 50 25 BPh₃ (2) 0.126   201 364 50 80 B(C₆F₅)₃ (2) 0.074   124 365 50 25 BPh₃ (10) 4.41  7,590 366 50 80 BPh₃ (10) 3.01  5,220 M_(w)(GPC): 17,900; PDI: 6 ^(a)TO: number of turnovers per metal center = (moles ethylene consumed, as determined by the weight of the isolated polymer or oligomers) divided by (moles catalyst). Calculations are based upon the exact amount of catalyst used. ^(b)M.W.: Molecular weight of the polymer or oligomers as determined by melt index (MI: g/10 min at 190° C.), GPC (molecular weights are reported versus polystyrene standards; conditions: Waters 150C, trichlorobenzene at 150° C., Shodex columns at −806MS 4G 734/602005, RI detector), and/or ¹H NMR (olefin end group analysis). ^(c)Total number of methyl groups per 1000 methylene groups as determined by ¹H NMR analysis. ^(d)Under the same reaction conditions (e.g., no Lewis acid present), nickel compounds 51-54 gave analogous results: no polymer was isolated, but the ¹H NMR spectra showed a —(CH₂)_(n)— resonance.

EXAMPLES 367-369 Cyclopentene Oligomerizations

General Procedure for Cyclopentene Oligomerizations. In the drybox under a nitrogen atmosphere, the nickel compound (0.03 mmol) was placed in a vial. Next, 5 mL of toluene was added to the vial followed by 1.3 mL of cyclopentene. B(C₆F₅)₃ (40 mg) was then added to the vial. The reaction mixture was mixed for 3 d on a vortexer and then removed from the drybox and added to 100 mL of stirring methanol. No polymer precipitated. GC analysis was carried out on the organic layer. The results are reported in Table 15 below.

TABLE 15 Cyclopentene Oligomerizations Ex. Cmpd GC Analysis 367 31a dimers through heptamers observed 368 32a dimers through heptamers observed 369 47b dimers through heptamers observed

EXAMPLES 370-375 Ethylene/Ethyl 4-Pentenoate Polymerizations

General Procedure for Ethylene/Ethyl 4-Pentenoate Polymerizations. In a nitrogen-filled drybox, the nickel compound (0.06 mmol) and the Lewis acid (5 equiv) were placed together in a glass insert. The insert was cooled to −30° C. in the drybox freezer. 5 mL of cold ethyl 4-pentenoate was added to the cold insert, and the insert was recooled in the drybox freezer. The cold inserts were removed from the drybox and placed under a nitrogen purge in a pressure tube, which was then sealed and pressurized to 6.9 MPa of ethylene and mechanically shaken for 18 h. The pressure was then released and the glass insert was removed from the pressure tube and the polymer was precipitated in MeOH, collected on a frit, and dried in vacuo. Characteristic NMR resonances of the copolymer include the 4.01 OCH₂ resonance in the ¹H NMR and the 59.7 OCH₂ resonance and ˜172.4 C═O resonances in the ¹³C NMR spectrum.

TABLE 16 Ethylene/Ethyl 4-Pentenoate (E-4-P) Polymerizations Lewis Temp Polymer Ex. Cmpd Acid (° C.) (g) DSC/GPC 370  3a BPh₃ 25 2.35  DSC: T_(m) = 111° C. ¹³C NMR: 0.59 mole percent E-4-P Incorp.; Branching per 1000 CH₂'s: Total methyls (27.3), Methyl (23.7), Ethyl (1.7), Propyl (0), Butyl (0.8), Amyl (2.4), Hex and greater and end of chains (5.4), Am and greater and end of chains (1.9), Bu and greater and end of chains (1.8) 371 21a BPh₃ 25 0.586 DSC: T_(m) = 115° C. ¹³C NMR: 0.26 mole percent E-4-P Incorp.; Branching per 1000 CH₂'s: Total methyls (25.0), Methyl (19.3), Ethyl (2.1), Propyl (0.0), Butyl (1.2), Amyl (0.3), Hex and greater and end of chains (3.1), Am and greater and end of chains (4.1), Bu and greater and end of chains 3.6) 372  8a B(C₆F₅)₃ 25 0.254 DSC: T_(m) = 124° C., 96° C. ¹³C NMR: 0.64 mole percent E-4-P Incorp.; Branching per 1000 CH₂'s: Total methyls (47.8), Methyl (35.8), Ethyl (3.7), Propyl (0.0), Butyl (3.1), Amyl (3.8), Hex and greater and end of chains (8.7), Am and greater and end of chains (10.2), Bu and greater and end of chains (8.3) 373  3a BPh₃ 80 0.468 ¹³C NMR: 1.94 mole percent E-4-P Incorp.; Branching per 1000 CH₂'s: Total methyls (67.0), Methyl (50.7), Ethyl (6.3), Propyl (0.0), Butyl (3.7), Amyl (7.3), Hex and greater and end of chains (18.6), Am and greater and end of chains (8.4), Bu and greater and end of chains (9.9) 374 21a BPh₃ 80 0.312 ¹³C NMR: 1.67 mole percent E-4-P Incorp.; Branching per 1000 CH₂'s: Total methyls (73.9), Methyl (47.9), Ethyl (9.2), Propyl (0.0), Butyl (0.0), Amyl (6.1), Hex and greater and end of chains (16.2), Am and greater and end of chains (15.7), Bu and greater and end of chains (16.8) 375  8a B(C₆F₅)₃ 80 0.232 GPC (THF, 35° C.): M_(w) = 5,130, PDI = 1.7; DSC: T_(m): 117° C., 46° C. ¹H NMR: 1.6 mole percent E-4-P Incorp.; Branching per 1000 CH₂'s: Total methyls (94)

EXAMPLES 376-381 General Procedure for Ethylene Polymerizations of Table 17

Ethylene Polymerizations in the Parr® Reactor

Procedure. Prior to conducting the polymerization, the Parr® reactor flushed with nitrogen, heated under vacuum overnight, and then allowed to cool to room temperature. In the drybox, a glass vial was loaded with the nickel compound, Lewis acid and solvent and then capped with a rubber septum. The solution of the nickel complex and Lewis acid was then transferred to a 100 mL Parr reactor under vacuum, and the reactor was pressurized with ethylene and the reaction mixture was mechanically stirred. After the stated reaction time, the ethylene pressure was released, and the polymer was precipitated by adding the reaction mixture to a solution of MeOH (˜100 mL) and concentrated HCl (˜1-3 mL). The polymer was then collected on a frit and rinsed with HCl, MeOH, and acetone. The polymer was transferred to a pre-weighed vial and dried under vacuum overnight. The polymer yield and characterization were then obtained.

TABLE 17 Ethylene Polymerizations in the Parr Reactor (0.02 mmol Cmpd, Trichlorobenzene (35 mL)) Time Press. Lewis Acid M.W.^(b) (MI, GPC, Total Ex. Cmpd (h) (MPa) (equiv) PE(g) PE(TO)^(a) and/or ¹H NMR) Me^(c) 376 6a 9.9 5.5 B(C₆F₅)₃/2 7.46 12,400  M_(n)(¹H):no olefins 34.4 377 6a 0.5 5.5 B(C₆F₅)₃/2 3.5 5,940 M_(n)(¹H):no olefins 40.3 378 6a 6.5 5.5 B(C₆F₅)₃/2 9.30 15,500  M_(n)(¹H):no olefins 39.2 379 6a 4.8 1.4 B(C₆F₅)₃/2 0.26   394 M_(n)(¹H):no olefins 32.6 380 3a 6.0 3.5 BPh₃/5 3.57 5,560 M_(n)(¹H):no olefins 19.1 381 6a 6.6 3.5 B(C₆F₅)₃/5 1.52 2,480 M_(n)(¹H):no olefins 29.0 ^(a)TO: number of turnovers per metal center = (moles ethylene consumed, as determined by the weight of the isolated polymer or oligomers) divided by (moles catalyst). Calculations are based upon the exact amount of catalyst used. ^(b)M.W.: Molecular weight of the polymer or oligomers as determined by melt index (MI: g/10 min at 190° C.), GPC (molecular weights are reported versus polystyrene standards; conditions: Waters 150C, trichlorobenzene at 150° C., Shodex columns at −806MS 4G 734/602005, RI detector), and/or ¹H NMR (olefin end group analysis). ^(c)Total number of methyl groups per 1000 methylene groups as determined by ¹H NMR analysis. ^(d)Under the same reaction conditions (e.g., no Lewis acid present), nickel compounds 51-54 gave analogous results: no polymer was isolated, but the ¹H NMR spectra showed a —(CH₂)_(n)— resonance.

EXAMPLES 382-437 General Procedure for Ethylene (28-35 kPa)

Polymerizations of Table 18

Procedure. In the drybox, a glass Schlenk flask was loaded with the nickel compound, Lewis acid, solvent and a stir bar. The flask was then capped with a rubber septum and the stopcock was closed prior to removing the flask from the drybox. The flask was then attached to the ethylene line where it was evacuated and backfilled with ethylene. The reaction mixture was stirred under ethylene for the stated reaction time, the ethylene pressure was then released, and the polymer was precipitated by adding the reaction mixture to a solution of MeOH (˜100 mL) and concentrated HCl (˜1-3 mL). The polymer was then collected on a frit and rinsed with MeOH. The polymer was transferred to a pre-weighed vial and dried under vacuum overnight. The polymer yield and characterization were then obtained.

TABLE 18 Ethylene Polymerizations at 28-35 kPa Ethylene Lewis Acid Time Ex. Cmpd (equiv) (h) Solvent (mL)^(b) PE(g) PE(TO) 382  1a B(C₆F₅)₃/20 25.0 Toluene (35) ^(a) ^(a) 383  1a MAO-IP/90 0.5 Toluene (35) 0.924 1,040   Description: White rubbery solid. 384  2a MAO-IP/86 0.5 Toluene (35) 0.534 577 Description: White, soft, slightly rubbery solid. 385  3a BPh₃/5 26.3 Toluene (35) ^(a) ^(a) 386  3a BPh₃/20 23.5 Toluene (35) 0.662 787 Description: Slightly sticky, clear, colorless amorphous solid. ¹H NMR (C₆D₆, rt) 99.6 total Me/1000 CH₂ 387  3a BPh₃/50 23.5 Toluene (35) 0.110 131 Description: Clear, colorless sticky viscous oil. ¹H NMR (C₆D₆, rt) 98.6 total Me/1000 CH₂ 388  3a BPh₃/100 23.5 Toluene (35) 0.021  25 Description: Light yellow, clear amorphous solid/oil. ¹H NMR (C₆D₆, rt) 102.7 total Me/1000 CH₂ 389  3a B(C₆F₅)₃/20 32.4 Toluene (35) 0.042  50 Description: White powder. 390  3a BF₃.Et₂O/50 25.5 Toluene (35) ^(a) ^(a) 391  4a BPh₃/50 23.5 Toluene (35) 0.261 310 Description: Clear, amorphous gummy solid. ¹H NMR (C₆D₆, rt) 107.4 total Me/1000 CH₂ 392  4a BPh₃/100 37.2 Toluene (35) 0.797 950 Description: Soft, white powder/solid. 393  5a BPh₃/5 26.3 Toluene (35) ^(a) ^(a) 394  5a BPh₃/50 23.5 Toluene (35) 0.054  64 Description: White slightly sticky, partially amorphous solid. 395  5a BPh₃/50 26.4 Toluene (35) 0.065  77 Description: Clear/white partial powder/partial amorphous solid. 396  6a B(C₆F₅)₃/5 26.4 Toluene (35) 0.15  180 Description: Brown sticky amorphous solid. ¹H NMR (C₆D₆, rt): 105.4 Total Me/1000 CH₂ 397  6a B(C₆F₅)₃/20 26.4 Toluene (35) 7.38  8,760   Description: White, slightly rubbery or spongy powder. ¹³C NMR: Branching per 1000 CH₂'s. Total methyls (59.8), methyl (38.5), ethyl (10.4), propyl (1.6), butyl (2.4), hexyl and greater and end of chains (7.0), amy and greater and end of chains (7.9), butyl and greater and end of chains (9.3). 398  6a BPh₃/100 17.0 Toluene (35) 0.17  200 Description: White soft powder. 399  6a BF₃.Et₂O/50 25.5 Toluene (35) ^(a) ^(a) 400  6a Al(O-i-Pr)₃/20 22.4 Toluene (35) ^(a) ^(a) 401  6a PMAO-IP/28 25.1 Toluene (35) ^(a) ^(a) 402  7a B(C₆F₅)₃/20 24.1 Toluene (35) 1.04  1,180   Description: White powder. 403  8a B(C₆F₅)₃/5 25.4 Toluene (35) 1.45  1,730   Soft partial powder/partial amorphous solid. ¹H NMR (C₆D₆, rt): 118.3 Total Me/1000 CH₂ 404  8a BPh₃/100 17.0 Toluene (35) 0.016  19 Description: Tan powder. 405  8a B(C₆F₅)₃/20 23.1 Toluene (35) 2.82  3,350   Description: Brown amorphous sticky solid. ¹H NMR (C₆D₆, rt): 143.0 Total Me/1000 CH₂ 406  9a B(C₆F₅)₃/5 26.4 Toluene (35) 0.018  21 Description: Brown partial oil, partial amorphous solid. 407  9a B(C₆F₅)₃/20 23.1 Toluene (35) 6.99  8,300   Description: Brown amorphous sticky solid. ¹H NMR (C₆D₆, rt): 174.4 Totalt Me/1000 CH₂ 408 10a BPh₃/20 24.2 Toluene (35) 1.43  1,700   Description: White powder. 409 12a BPh₃/20 25.0 Toluene (35) 0.749 890 Description: White powder. 410 12a B(C₆F₅)_(3/10) 22.5 Toluene (35) ^(a) ^(a) 411 14a B(C₆F₅)_(3/20) 25.5 Toluene (35) 0.97  1,150   Description: White, stringy powder 412 15a B(C₆F₅)₃/10 22.5 Toluene (35) 0.106 126 Description: Slightly rubbery off-white solid. 413 17a B(C₆F₅)₃/20 25.5 Toluene (35) 2.08  2,470   Description: Soft white powder. 414 21a BPh₃/5 25.4 Toluene (35) 1.88  2,230   Description: White, somewhat rubbery powder. 415 21a BPh₃/20 26.4 Toluene (35) 1.73  2,060   Description: White powder. 416 21a BPh₃/50 26.4 Toluene (35) 0.631 750 Description: White powder. 417 21a BPh₃/100 21.4 1,2,4-TCB (20) 0.474 563 Description: White powder. 418 21b BPh₃/100 21.4 1,2,4-TCB(20) 0.156 185 419 22a BPh₃/100 37.2 Toluene (35) 0.777 920 Description: White powder. 420 23a BPh₃/20 26.0 Toluene (35) 0.409 473 Description: Almost clear, sticky amorphous oil/solid. 421 24a B(C₆F₅)₃/10 22.5 Toluene (35) ^(a) ^(a) 422 24a BPh₃/50 22.4 Toluene (35) 0.374 444 Description: White powder. 423 25a BPh₃/50 24.2 Toluene (35) 1.47  1,750   Description: White, slightly rubbery powder. 424 27a BPh₃/20 26.0 Toluene (35) 0.856 992 Description: Amorphous, slightly sticky, waxy, clear solid. ¹H NMR (C₆D₆, rt) 90.0 total Me/1000 CH₂ 425 30a B(C₆F₅)₃/20 24.2 Toluene (25) 0.65  770 Description: White powder. 426 34a B(C₆F₅)₃/20 23.1 Toluene (35) 5.75  6,830   Description: Tan amorphous solid. ¹H NMR (C₆D₆, rt) 182.0 Total Me/1000 CH₂. Mn˜1,980 427 36a BPh₃/20 25.6 Toluene (35) 1.32  1,570   Description: White powder. 428 36a B(C₆F₅)₃/10 24.3 Toluene (35) 0.11  130 Description: Tan powder. 429 37a BPh₃/20 23.8 Toluene (35) 0.486 576 430 38a BPh₃/20 26.0 Toluene (35) 0.024  28 Description: Clear, amorphous, very slightly sticky solid ¹H NMR (C₆D₆, rt) 91.2 total Me/1000 CH₂ 431 39a B(C₆F₅)₃/20 22.6 Toluene (20) 0.244 290 Description: White powder. 432 39a BPh₃/200 23.8 Toluene (35) ^(a) ^(a) 433 41a B(C₆F₅)₃/5 25.4 Toluene (35) 0.059  70 Description: White powder. 434 41a B(C₆F₅)₃/20 22.4 Toluene (35) 1.73  2,060   Description: White powder. 435 50  BPh₃/100 21.4 1,2,4-TCB (20) 1.06  1,260   Description: White powder. 436 52  BPh₃/100 21.4 1,2,4-TCB(20) 1.21  1,440   Description: White powder. 437 52  BPh₃/100 23.1 Toluene (35) 1.40  1,660   Description: White powder. ^(a)Only a trace of polymer or no polymer was isolated. ^(b)1,2,4-Trichlorobenzene is abbreviated as 1,2,4-TCB.

EXAMPLE 438 Ethylene Polymerization Using (acac)Ni(Et)PPh₃ Precursor at 6.9 MPa

In the drybox, a glass insert was loaded with (acac)Ni(Et)PPh₃ (26.9 mg, 0.06 mmol) and [2-(NaO)-3,5-(t-Bu)₂—C₆H₂—C(Me)═NAr (Ar=2,6-(i-Pr)₂—C₆H₃) 0.5 THF] (25.8 mg, 1 equiv). The insert was cooled to −35° C. in the drybox freezer, 5 mL of C₆D₆ was added to the cold insert, and the insert was cooled again. BPh₃ (29.1 mg, 2 equiv) was added to the cold solution, and the insert was then capped and sealed and cooled again. Outside of the drybox, the cold insert was placed under a nitrogen purge into the pressure tube. The pressure tube was sealed, placed under ethylene (6.9 MPa), and allowed to warm to rt as it was shaken mechanically for approximately 18 h. Polyethylene (16.5 g, 9,820 TO) was isolated as a powder following precipitation from methanol.

EXAMPLE 439 Ethylene Polymerization Using NiBr₂ Precursor at 28-35 MPa

The sodium salt of the ligand of Example 1 (1.01 g, 2.23 mmol), e.g.

was placed in a round bottom flask in the drybox together with 487 mg (2.23 mmol) of NiBr₂. THF (20 mL) was added and the solution was stirred for ˜2 months. The THF was removed in vacuo and the product was dissolved in CH₂Cl₂ and the resulting solution was filtered. The solvent was removed and the product was dried in vacuo. An orange powder (488 mg) was isolated. (In addition to CD₂Cl₂, the product was also soluble in C₆D₆. ¹H NMR spectra in both solvents were complex.)

In the drybox, a glass Schlenk flask was loaded with the resulting orange nickel compound (17 mg, ˜0.03 mmol), 35 mL of toluene and a stir bar. The flask was then capped with a rubber septum and the stopcock was closed prior to removing the flask from the drybox. The flask was then attached to the ethylene line where it was evacuated and backfilled with ethylene. MAO-IP (2 mL, ˜94 equiv) was added to the flask via cannula. The reaction mixture was stirred under ethylene for 3.5 h, the ethylene pressure was then released, and the polymer was precipitated by adding the reaction mixture to a solution of MeOH (100 mL) and concentrated HCl (˜1-3 mL). The polymer was then collected on a frit and rinsed with MeOH. The polymer was transferred to a pre-weighed vial and dried under vacuum overnight. A white polyethylene film (5.09 g, ˜6050 TO) was isolated.

EXAMPLES 440-468 Ligand Syntheses

Ligand syntheses and deprotonations were carried out according to the general procedures given below and under Examples 1-16 (see above) unless stated otherwise.

EXAMPLE 440 [2-(OH)-3,5—Cl₂—C₆H₂]—C(Me)═NAr [Ar=2,6-(i-Pr)₂—C₆H₃]

The general procedure for imine synthesis was followed using 10.03 g (48.9 mmol) of 3′, 5′-dichloro-2′-hydroxyacetophenone and 11.27 g (1.30 equiv) of 2,6-diisopropylaniline. A yellow powder (15.35 g, 86.2%) was isolated: ¹H NMR (CDCl₃) δ 7.46 (d, 1, Ar′: H), 7.44 (d, 1, Ar′: H), 7.14 (m, 3, Ar: H), 2.64 (septet, 2, CHMe₂), 2.12 (s, 3, N═C(Me)), 1.08 and 1.04 (d, 6 each, CHMeMe′).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.59 equiv of THF coordinated.

EXAMPLE 441 [2-(OH)-3,5-Cl₂—C6H₂]—C(Me)═NAr [Ar=2,6-Me₂—C₆H₃]

The general procedure for imine synthesis was followed using 10.681 g (52.1 mmol) of 3′, 5′-dichloro-2′-hydroxyacetophenone and 8.21 g (1.30 equiv) of 2,6-dimethylaniline. A yellow powder (7.61 g, 47.4) was isolated: ¹H NMR (CDCl₃) δ 7.57 (d, 1, Ar′: H), 7.52 (d, 1, Ar′: H), 7.15 (d, 2, Ar: H_(m)), 7.08 (t, 1, Ar: H_(p)), 2.21 (s, 3, N═CMe), 2.10 (s, 6, Ar: Me).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.59 equiv of THF coordinated.

EXAMPLE 442 [2-(OH)-3,5—Cl₂—C₆H₂]—C(Me)═NAr [Ar=2-(t-Bu)—C₆H₄]

The general procedure for imine synthesis was followed using 10.41 g (50.8 mmol) of 3′, 5′-dichloro-2′-hydroxyacetophenone and 9.85 g (1.30 equiv) of 2-t-butylaniline. A yellow powder (15.30 g, 89.6%, 2 crops) was isolated: ¹H NMR (CDCl₃ ) δ 7.55 (d, 1, Ar′: H), 7.52 (d, 1, Ar′: H), 7.50 (d, 1, Ar: H), 7.25 (t, 1, Ar: H), 7.22 (t, 1, Ar: H), 6.52 (d, 1, Ar: H), 2.31 (s, 3, Me), 1.36 (s, 9, CMe₃).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.16 equiv of THF coordinated.

EXAMPLE 443 [2-(OH)-3,5-Br₂—C₆H₂]—CH═NAr [Ar=2,6-(i-Pr)₂—C₆H₃]

The general procedure for imine synthesis was followed using 3.23 g (11.5 mmol) of 3,5-dibromosalicylaldehyde and 2.66 g (1.30 equiv) of 2,6-diisopropylaniline. A yellow powder (3.10 g, 61.4%) was isolated: ¹H NMR (CDCl₃) 8.21 (s, 1, N═CH), 7.81 (d, 1, Ar′: H), 7.45 (d, 1, Ar′: H), 7.22 (s, 3, Ar: H), 2.94 (septet, 2, CHMe₂), 1.18 (d, 12, CHMe₂).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.7 equiv of THF coordinated.

EXAMPLE 444 [2-(OH)-3,5-Br₂—C₆H₂]—C(Me)═NAr [Ar=2,6-(i-Pr)₂—C₆H₃]

The general procedure for imine synthesis was followed using 10.84 g (36.9 mmol) of 3′,5′-dibromo-2′-hydroxyacetophenone and 8.50 g (1.30 equiv) of 2,6-diisopropylaniline. A yellow powder (13.16 g, 78.7%) was isolated: ¹H NMR (CDCl₃) δ 7.83 (d, 1, Ar′: H), 7.73 (d, 1, Ar′: H), 7.26 (m, 3, Ar: H), 2.76 (septet, 2, CHMe₂), 2.24 (s, 3, Me), 1.19 and 1.18 (d, 6 each, CHMeMe′).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.54 equiv of THF coordinated.

EXAMPLE 445 [2-(OH)-3,5-Br₂—C₆H₂]—C(Me)═NAr [Ar=2,6-Me₂—C6H₃]

The general procedure for imine synthesis was followed using 10.43 g (35.5 mmol) of 3′,5′-dibromo-2′-hydroxyacetophenone and 5.59 g (1.30 equiv) of 2,6-dimethylaniline. A yellow powder (11.6 g) was isolated. The ¹H NMR spectrum of the initially isolated product showed that it was contaminated by the hydroxyacetophenone. The product was repurified by washing with more methanol, dissolving in CH₂Cl₂ and drying over Na₂SO₄, filtering and evaporating the solvent. A yellow powder (5.60 g) was isolated. The product mixture was now 12.7% of the starting aldehyde. The remainder is the desired imine product: ¹H NMR (CDCl₃) δ 7.78 (d, 1, Ar′: H), 7.71 (d, 1, Ar′: H), 7.11 (d, 2, Ar: H_(m)), 7.05 (t, 1, Ar: H_(p)), 2.18 (s, 3, N═CMe), 2.05 (s, 6, Ar: Me).

The sodium salt was synthesized according to the above general procedure and is clean and consistent with the desired product (no hydroxyacetophenone impurities present): ¹H NMR (THF-d₈): 0.81 equiv of THF coordinated.

EXAMPLE 446 [2-(OH)-3,5-Br₂—C₆H₂]—C(Me)═NAr [Ar=2-(t-Bu)—C₆H₄]

The general procedure for imine synthesis was followed using 10.04 g (34.2 mmol) of 3′,5′-dibromo-2′-hydroxyacetophenone and 6.63 g (1.30 eguiv) of 2-t-butylaniline. A yellow powder (12.63 g, 86.9%) was isolated: ¹H NMR (CDCl₃) δ 7.81 (d, 1, Ar′: H), 7.72 (d, 1, Ar′: H), 7.51 (d, 1, Ar: H), 7.27 (t, 1, Ar: H), 7.22 (t, 1, Ar: H), 6.51 (d, 1, Ar: H), 2.31 (s, 3, N═CMe), 1.37 (s, 9, CMe₃).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): trace THF coordinated.

EXAMPLE 447 [2-(OH)-3,5-(t-Bu)₂C₆H₂]—CH═NAr [Ar=2-(t-Bu)—C₆H₄]

The general procedure for imine synthesis was followed using 4.12 g (17.6 mmol) of 3,5,-di-t-butyl-2-hydroxybenzaldehyde and 3.15 g (1.20 equiv) of 2-t-butylaniline. The desired imine product was isolated as a yellow powder: ¹H NMR (CDCl₃) δ 8.36 (s, 1, N═CH), 7.40 (d, 1, Ar′: H), 7.36 (d, 1, Ar: H), 7.18 (t, 1, Ar: H), 7.15 (d, 1, Ar′: H), 7.13 (t, 1, Ar: H), 6.80 (d, 1, Ar: H), 1.42, 1.37 and 1.26 (s, 9 each, CMe₃, C′Me₃, C″Me₃).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 1 equiv of THF coordinated.

EXAMPLE 448 [2-(OH)-3,5-(t-Bu)₂C₆H₂]—CH═NAr [Ar=2-Aza—C₅H₄]

The general procedure for imine synthesis was followed using 3.02 g (12.9 mmol) of 3,5-di-t-butyl-2-hydroxybenzaldehyde and 1.46 g (1.20 equiv) of 2-amino-pyridine. An orange powder (0.552 g, 13.8%) was isolated: ¹H NMR (CDCl₃) δ 9.47 (s, 1, N═CH), 8.51 (m, 1, Py: H), 7.77 (m, 1, Py: H), 7.48 (d, 1, Ar′: H), 7.35 (d, 1, Ar′: H), 7.33 (m, 1, Py: H), 7.20 (m, 1, Py: H), 1.48 (s, 9, CMe₃), 1.34 (s, 9, C′Me₃).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.2 equiv of THF coordinated.

EXAMPLE 449 [2-(OH)-3,5-(t-Bu)₂C₆H₂]—CH═NAr [Ar=2-Aza-6-Me—C₅H3]

The general procedure for imine synthesis was followed using 3.46 g (14.7 mmol) of 3,5-di-t-butyl-2-hydroxybenzaldehyde and 1.91 g (1.20 equiv) of 2-amino-3-picoline. The first crop isolated as a precipitate from methanol was an orange powder (1.18 g). This crop was not clean and was discarded, although some of the desired product was present as a minor component. The remaining methanol solution was allowed to slowly evaporate to give orange crystals. The methanol was decanted off of the crystals and the standard work-up procedure was followed. An orange powder (0.813 g) was isolated, and the NMR spectrum of this second crop was clean and consistent with the desired product: ¹H NMR (CDCl₃) δ 9.45 (s,1, N═CH), 8.34 (d, 1, Py: H), 7.60 (d, 1, Py: H), 7.48 (d, 1, Ar′: H), 7.38 (d, 1, Ar′: H), 7.13 (dd, 1, Py: H), 2.49 (s, 3, Me), 1.5 (s, 9, CMe₃), 1.34 (s, 9, C′Me₃).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.4 equiv of THF coordinated.

EXAMPLE 450 [2-(OH)-3,5-(t-Bu)₂C₆H₂]—CH═NCHPh₂

The general procedure for imine synthesis was followed using 3.00 g (12.8 mmol) of 3,5-di-t-butyl-2-hydroxybenzaldehyde and 2.60 g (1.11 equiv) of aminodiphenylmethane. A yellow powder (2.85 g, 55.7%) was isolated: ¹H NMR (CDCl₃) δ 8.50 (s, 1, N═CH), 7.42 (d, 1, Ar′: H), 7.40-7.23 (m, 10, CPh₂), 7.11 (d, 1, Ar′: H), 5.63 (s, 1, CHPh₂), 1.48 and 1.32 (s, 9 each, CMe₃ and C′Me₃).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 1 equiv of THF coordinated.

EXAMPLE 451 [2-(OH)-3,5-(t-Bu)₂C₆H₂]—CH═NR [R=1,2,3,4-tetrahydro-1-naphthyl]

The general procedure for imine synthesis was followed using 3.08 g (13.1 mmol) of 3,5-di-t-butyl-2-hydroxybenzaldehyde and 2.32 g (1.20 equiv) of 1,2,3,4-tetrahydro-1-naphthylamine. A yellow powder (3.97 g, 83.4%) was isolated: ¹H NMR (CDCl₃) δ 8.45 (s, 1, N═CH), 7.39 (d, 1, Ar′: H), 7.22-7.04 (m, 5, Ar: H, Ar′: H), 4.53 (m, 1, NCHCH₂CH₂CH₂), 2.88 (m, 2, NCHCH₂CH₂CH₂), 2.14-1.79 (m, 4, NCHCH₂CH₂CH₂), 1.42 (s, 9, CMe₃), 1.32 (s, 9, C′Me₃).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d8): 0.6 equiv of THF coordinated.

EXAMPLE 452 [2-(OH)-3,5-(NO₂)₂C₆H₂]—CH═NAr [Ar=2-(t-Bu)—C₆H₄]

The general procedure for imine synthesis was followed using 3.05 g (14.4 mmol) of 3,5-dinitrosalicylaldehyde and 2.57 g (1.20 equiv) of 2-t-butylaniline. A yellow powder was isolated: ¹H NMR (CDCl₃) δ 8.94 (s, 1, N═CH), 8.54 (d, 1, Ar′: H), 8.50 (d, 1, Ar′: H), 7.49 (d, 1, Ar: H), 7.35 (t, 1, Ar: H), 7.31 (t, 1, Ar: H), 7.02 (d, 1, Ar: H), 1.40 (s, 9 CMe₃).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.79 equiv of THF coordinated.

EXAMPLE 453 [2-(OH)-3,5-(NO₂)₂C₆H2]—CH═NAr [Ar=2-Me-6-Cl—C₆H₃]

The general procedure for imine synthesis was followed using 1.56 g (7.33 mmol) of 3,5-dinitrosalicylaldehyde and 1.25 g (1.20 equiv) of 2-chloro-6-methylaniline. An orange powder (1.35 g, 55.0%) was isolated: ¹H NMR (CDCl₃) δ 15.96 (br s, 1, OH), 8.71 (s, 1, N═CH), 8.60 (d, 1, H_(aryl)), 7.50-7.15 (m, 4, H_(aryl)), 2.36 (s, 1, Me).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.14 equiv of THF coordinated.

EXAMPLE 454 [2-(OH)-3,5-(NO₂)₂C₆H₂]—CH═NR [R=1,2,3,4-tetrahydro-1-naphthyl]

The general procedure for imine synthesis was followed using 3.07 g (14.5 mmol) of 3,5-dinitrosalicylaldehyde and 2.55 g (1.20 equiv) of 1,2,3,4-tetrahydro-1-naphthylamine. A yellow powder (4.31 g, 87.1%) was isolated: ¹H NMR (CDCl₃) δ 8.98 (d, 1, Ar′: H), 8.36 (d, 1, Ar′: H), 8.07 (d, 1, Ar: H), 7.36 (m, 1, Ar: H), 7.27 (m, 3, N═CH and Ar: H), 7.15 (d, 1, Ar: H), 5.04 (m, 1, NCHCH₂CH₂CH₂), 2.90 (m, 2, NCHCH₂CH₂CH₂), 2.26, 1.97 and 1.87 (m′s, 2, 1 and 1 each, NCHCH₂CH₂CH₂).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.11 equiv of THF coordinated.

EXAMPLE 455 [2-(OH)-3,5-I₂—C₆H₂]—CH═NAr [Ar=2,6-(i-Pr)₂—C₆H₃]

The general procedure for imine synthesis was followed using 6.00 g (16.0 mmol) of 3,5-diiodosalicylaldehyde and 3.70 g (1.31 equiv) of 2,6-diisopropylaniline. A yellow powder (7.93 g, 93.0%) was isolated: ¹H NMR (CDCl₃) δ 8.14 (d, 1, Ar′: H), 8.10 (s, 1, N═CH), 7.60 (d, 1, Ar′: H), 7.20 (m, 3, Ar: H), 2.92 (septet, 2, CHMe₂), 1.18 (d, 12, CHMe₂).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.67 equiv of THF coordinated.

EXAMPLE 456 [2-(OH)-4,6-(OMe)₂—C₆H₂]—CH═NAr [Ar=2,6-(i-Pr)H—C₆H3]

The general procedure for imine synthesis was followed using 5.05 g (27.7 mmol) of 4,6-dimethoxysalicylaldehyde and 5.90 g (1.20 equiv) of 2,6-diisopropylaniline. A yellow powder (3.59 g, 38.0%) was isolated: ¹H NMR (CDCl₃) δ 8.58 (s, 1, N═CH), 7.18 (s, 3, Ar: H), 6.13 (d, 1, Ar′: H), 5.92 (d, 1, Ar′: H), 3.84 (s, 3, OMe), 3.80 (s, 3, OMe′), 3.03 (septet, 1, CHMe₂), 1.19 (d, 12, CHMe₂).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): No THF coordinated.

EXAMPLE 457 [2-Hydroxynaphthyl]—CH═NAr [Ar=2,6-Br₂-4-F—C₆H₂]

The general procedure for imine synthesis was followed using 29.8 g (173 mmol) of 2-hydroxy-1-naphthaldehyde and 52.0 g (193 mmol) of 2,6-dibromo-4-fluoroaniline. A yellow powder (62.1 g, 84.9%, 2 crops) was isolated: ¹H NMR (CDCl₃ ) δ 9.40 (s, 1, N═CH), 8.09 (d, 1, Ar′: H), 7.92 (d, 1, Ar′: H), 7.81 (d, 1, Ar′: H), 7.55 (t, 1, Ar′: H), 7.43 (d, 2, Ar: H), 7.40 (t, 1, Ar′: H), 7.25 (d, 1, Ar′: H).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.66 equiv of THF coordinated.

EXAMPLE 458 [2-Hydroxynaphthyl]—CH═NAr [Ar=2-Aza-6-Me—C₅H₃]

The general procedure for imine synthesis was followed using 3.44 g (20.0 mmol) of 2-hydroxy-1-naphthaldehyde and 2.59 g (1.20 equiv) of 2-amino-3-picoline. A yellow-orange powder (4.51 g, 86.0%) was isolated: ¹H NMR (CDCl₃) δ 9.94 (d, 1, H_(aryl)), 8.27 (d, 1, N═CH), 8.09 (d, 1, H_(aryl)), 7.68 (d, 1, H_(aryl)), 7.54 (d, 1, H_(aryl)), 7.51 (d, 1, H_(aryl)), 7.44 (t, 1, H_(aryl)), 7.24 (t, 1, H_(aryl)), 7.02 (t, 1, H_(aryl)), 6.85 (d, 1, H_(aryl)), 2.44 (s, 3, Me).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.1 equiv of THF coordinated.

EXAMPLE 459 [2-Hydroxynaphthyl]—CH═NAr [Ar=2-(t-Bu)—C₆H₄]

The general procedure for imine synthesis was followed using 10.19 g (59.2 mmol) of 2-hydroxy-1-naphthaldehyde and 10.60 g (1.20 equiv) of 2-t-butylaniline. A yellow powder (10.8 g, 60.4%) was isolated: ¹H NMR (CDCl₃) δ 9.27 (d, 1, N═CH), 8.18 (d, 1, H_(aryl)), 7.88 (d, 1, H_(aryl)), 7.79 (d, 1, H_(aryl)), 7.55 (t, 1, H_(aryl)) 7.52 (d, 1, H_(aryl)) 7.39 (t, 1, H_(aryl)) 7.37 (t, 1, H_(aryl)) 7.30 (t, 1, H_(aryl)) 7.21 (d, 1, H_(aryl)) 7.19 (d, 1, H_(aryl)), 1.52 (s, 9, CMe₃).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.48 equiv of THF coordinated.

EXAMPLE 460 (Ar)(H)N—C(Me)═CH—C(O)—Ph [Ar=2,6-(i-Pr)₂—C6H₃]

The general procedure for imine synthesis was followed using 5.17 g (31.9 mmol) of 1-benzoylacetone and 7.35 g (1.30 equiv) of 2,6-diisopropylaniline. After 2 days, no precipitate formed from the methanol solution. However, slow evaporation of the methanol yielded single crystals, which were isolated and washed with a small amount of additional methanol. The standard work-up procedure was then followed to yield a white powder (2.56 g, 25.0%): ¹H NMR (CDCl₃) δ 7.89 (d, 2, H_(aryl)), 7.38 (m, 3, H_(aryl)) 7.25 (t, 1, H_(aryl)), 7.12 (d, 1, H_(aryl)), 5.86 (s, 1, ═CH), 3.02 (septet, 2, ChMe₂), 1.71 (s, 3, N—C(Me)), 1.17 and 1.11 (d, 6 each, CHMeMe′); ¹³C NMR (CDCl₃) δ 188.4 (C(O)), 165.0 (N—C(Me)), 146.2 (Ar: C_(o)), 140.0 and 133.5 (Ph: C_(ipso); Ar: C_(ipso))) 130.8 and 128.3 (Ar: C_(p); Ph: C_(p)), 128.1, 127.1 and 123.5 (Ph: C_(o), C_(m); Ar: C_(m)), 92.1 (C(Me)═CH), 28.5 (CHMe₂), 24.6 and 22.7 (CHMeMe′), 19.7 (N—C(Me)).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.66 equiv of THF coordinated.

EXAMPLE 461

A 200 mL sidearm flask was charged with 5.0 g (42 mmol, 1.0 equiv) of 2-hydroxybenzonitrile, 5.6 g (63 mmol, 1.5 equiv) of 2-amino-2-methylpropanol, 0.29 g (2.1 mmol, 0.05 equiv) of ZnCl₂, and 90 mL of chlorobenzene. The reaction mixture was heated to reflux under N₂ atmosphere for 24 h. After this time, reflux was discontinued, the flask was cooled to ambient temperature, and most of the volatile materials were removed using a rotary evaporator. The resulting residue was dissolved in ˜100 mL of CH₂Cl₂, transferred to a separatory funnel, and washed with 3×50 mL of H₂O. The combined H₂O washings were back extracted with 30 mL of CH₂Cl₂, and the combined CH₂Cl₂ extracts were then dried over Na₂SO₄, filtered and evaporated to yield a brown oil which was purified by flash chromatography (SiO₂, eluting with 5:1 hexanes:EtOAc), to yield 6.3 g (78%) of the desired product: ¹H NMR (CDCl₃) δ 12.2 (br s, 1, OH), 7.6 (m, 1, H_(aryl)), 7.4 (m, 1, H_(aryl)), 7.06 (m, 1, H_(aryl)), 6.92 (m, 1, H_(aryl)), 4.14 (s, 2, CH₂), 1.44 (s, 6, CMe₂).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.20 equiv of THF coordinated.

EXAMPLE 462 (4-Me—C₆H₄—N═P(Ph)₂—CH₂—(Ph)₂P═N—C₆H₄-4-Me)

See Phosphorus, Sulfur, and Silicon 1990, 47, 401. A 100-mL 3-neck round-bottomed flask was fitted with a condenser, a nitrogen inlet and an addition funnel. It was charged with 2.64 g (6.87 mmol) of bis(diphenylphosphino)methane (DPPM) dissolved in 17 mL of benzene. The addition funnel was charged with 1.86 g (14.0 mmol) of 4-Me—C₆H₄—N₃ (prepared from p-toluidine hydrochloride, sodium nitrite and sodium azide, see Ugi, I; Perlinger, H.; Behringer, L. Chemische Berichte 1958, 91, 2330) dissolved in ca. 7-10 mL of benzene. The DPPM solution was heated to 60° C. and the aryl azide solution slowly added to the reaction mixture. As the addition occurred, nitrogen was evolved. After the addition was completed, the reaction mixture was kept an additional 4 h at 60° C. The solvent was then removed in vacuo, and the solid was collected, washed with 2×15 mL of hexane and dried in vacuo. The yield was 3.75 g (92%): ¹H NMR (CDCl₃) δ 7.72 (m, 8, PPh₂: H_(o)) 7.41 (t, 4, PPh₂: H_(p)), 7.29 (t, 3, PPh₂: H_(m)), 6.83 (d, 4, NAr: H_(m)), 6.52 (d, 4, NAr: H_(o)), 3.68 (t, 2, J_(HP)=14.2, PCH₂P), 2.21 (s, 6, NAr: Me).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.39 equiv of THF coordinated.

EXAMPLE 463 (2-Me—C₆H₄—N═P(Ph)₂—CH—(Ph)₂P═N—C₆H_(4—2)-Me)

A 100-mL 3-neck round-bottomed flask was fitted with a condenser, a nitrogen inlet and an addition funnel. It was charged with 3.0 g (7.80 mmol) of bis(diphenylphosphino)methane (DPPM) dissolved in 20 mL of toluene. The addition funnel was charged with 2.11 g (15.8 mmol) of 2-Me—C₆H₄—N₃ (prepared from o-toluidine hydrochloride, sodium nitrite and sodium azide) dissolved in ca. 12 mL of toluene. The DPPM solution was heated to 60° C. and the aryl azide solution slowly added to the reaction mixture. As the addition occurred, nitrogen was evolved. After the addition was completed, the reaction mixture was kept an additional 4 h at 60° C. The solvent was then removed in vacuo, the solid was collected and recrystallized from Et₂O/hexane. The yield was 2.70 g (58%). ¹H NMR (CDCl₃) δ 7.68 (m, 8, PPh₂: H_(o)), 7.38 (t, 4, PPh₂: H_(p)), 7.25 (t, 8, PPh₂: H_(m)), 7.09 (d, 2, NAr: H_(m)′) 6.76 (t, 2, NAr: H_(m)), 6.23 (t, 2, NAr: H_(p)), 6.23 (d, 2, NAr: H_(o)) 3.87 (t, 2, J_(HP)=13.5, PCH₂P), 2.29 (s, 6, NAr: Me).

The sodium salt was synthesized according to the above general procedure: ¹H NMR (THF-d₈): 0.59 equiv of THF coordinated.

EXAMPLE 464 Lithium 5-Methyl-2-Thiophenecarboxylate

The sodium salt was synthesized from commercially available 5-methyl-2-thiophenecarboxylic acid according to the above general procedure and the cation was exchanged with an excess of lithium chloride to improve product solubility: ¹H NMR (THF-d₈): 0.25 equiv of THF coordinated.

EXAMPLE 465 Cy₂PCH₂CH(CH₃)SLi

A 100-mL Schlenk flask was charged with 1.28 g (6.28 mmol) of PCy₂Li (prepared from PCy₂H and n-BuLi) dissolved in 20 mL of THF. The flask was cooled to −78° C. and propylene sulfide (520 mg, 7.01 mmol) was vacuum transferred onto the lithium salt solution. The reaction mixture was kept at −78° C. for 45 min. The dry ice/acetone bath was then removed and the yellowish solution was allowed to warm to ambient temperature. After an additional 20 min, the solvent was removed in vacuo. The solid was washed three times with 30 mL of hexane and dried in vacuo. The yield was 1.37 g (78%). ¹H NMR (THF-d₈, 300 MHz, 23° C.) δ 2.80 (m, 1, CH), 1.31 (d, 3, J=6 Hz, CH₃), 1-2 (m, 24, Cy₂, PCH₂); ³¹P NMR: δ −7.6.

EXAMPLE 466 Sodium 2,3,5,6-Tetrachloro-4-Pyridinethiolate

The sodium salt was synthesized according to the above general procedure from the commercially available 2,3,5,6-tetrachloro-4-pyridinethiol.

EXAMPLE 467 Sodium 2,5-Dimethylpyrrole

The sodium salt was synthesized according to the above general procedure from the commercially available 2,5-dimethylpyrrole: ¹H NMR (THF-d₈): No THF coordinated.

EXAMPLE 468 Sodium 2,6-Dibromo-4-Methylanilide

The sodium salt was synthesized according to the above general procedure from the commercially available 2,6-dibromo-4-methylaniline: ¹H NMR (THF-d₈): 0.5 equiv THF coordinated.

EXAMPLES 469-498

Complexes 21 through 49 were synthesized according to the general procedure for the synthesis of allyl initiators (see above under Examples 17-40).

EXAMPLE 469

Complex 21a. Two equiv (2.77 g, 6.45 mmol) of the sodium salt of the ligand were reacted with one equiv (1.53 g, 3.22 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 2.94 g (87.4% yield) of a yellow powder: ¹H NMR (C₆D₆) δ 7.39 (d, 1, Ar′: H), 7.29 (d, 1, Ar′: H), 7.0-6.9 (m, 3, Ar: H), 4.00 (m, 1, HH′CC(CO₂Me)C′HH′), 3.57 and 2.86 (septet, 1 each, CHMe₂ and C′HMe₂), 3.25 (s, 3, OMe), 2.86 (s, 1, HH′CC(CO₂Me)C′HH′), 1.92 (m, 1, HH′CC(CO₂Me)C′HH′), 1.47 (s, 3, N═CMe), 1.34, 1.18, 0.89 and 0.79 (d, 3 each, CHMeMe′ and C′HMeMe′), 1.12 (s, 1 each, HH′CC(CO₂Me)C′HH′).

EXAMPLE 470

Complex 21b. Two equiv (720 mg, 1.68 mmol) of the sodium salt of the ligand were reacted with one equiv (225 mg, 0.834 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CCHCH₂) to give 599 mg (77.6% yield) of a yellow powder: ¹H NMR (CDCl₃) δ 7.39 (d, 1, Ar′: H), 7.35 (d, 1, Ar′: H), 7.13-7.00 (m, 3, Ar: H), 5.78 (m, 1, H₂CCHC′H₂), 3.66 and 3.07 (m, 1 each, CHMe₂ and C′HMe₂), 3.21, 2.64, 1.44 and 1.11 (d, 1 each, HH′CCHC′HH′), 1.99 (s, 3, N═CMe), 1.31, 1.26, 1.07 and 0.99 (d, 3 each, CHMeMe′ and C′HMeMe′); ¹³C NMR (CDCl₃) δ 168.7 (N═CMe), 159.5, 150.0, 137.7, 137.0, 131.8, 128.7, 127.9, 125.9, 123.8, 123.3, 120.9, 117.1., 113.1 (Ar: C_(o), C_(o)′, C_(m), C_(m)′, C_(p), Ar′: C_(o), C_(o)′, C_(m), C_(m)′, C_(p), H₂CCHCH₂), 59.4 and 52.8 (H₂CCHC′H₂), 28.3 and 27.8 (CHMe₂, C′HMe₂), 24.1, 23.64, 23.54 and 23.4 (CHMeMe′ and C′HMeMe′), 20.3 (N═CMe).

EXAMPLE 471

Complex 22a. Two equiv (809 mg, 2.14 mmol) of the sodium salt of the ligand were reacted with one equiv (508 mg, 1.07 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 792 mg (79.6% yield) of a yellow powder: ¹H NMR (C₆D₆) δ 7.57 (d, 1, Ar′: H), 7.30 (d, 1, Ar′: H), 7.0-6.9 (m, 3, Ar: H), 4.10 (m, 1, HH′CC(CO₂Me)C′HH′), 3.38 (s, 3, OMe), 2.69 (s, 1, HH′CC(CO₂Me)C′HH′), 2.02 and 2.12 (s, 3, Ar: Me, Me′), 1.89 (m, 1, HH′CC(CO₂Me)C′HH′), 1.45 (s, 3, N═CMe), 1.35 (s, 1, HH′CC(CO₂Me)C′HH′)

EXAMPLE 472

Complex 23a. Two equiv (1.56 g, 4.20 mmol) of the sodium salt of the ligand were reacted with one equiv (1.00 g, 2.10 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 1.35 g (65.3% yield) of a yellow powder: According to the ¹H NMR spectrum, two isomers (t-Bu group positioned syn and anti to the CO₂Me group) are present in a 1:1 ratio. ¹H NMR (C₆D₆) δ 7.6-6.5 (m, 8, H_(aryl)), 4.16 and 4.01 (s, 1 each, HH′CC(CO₂Me)C′HH′ of each isomer), 3.42 and 3.42 (s, 3 each, OMe of each isomer), 2.82 and 2.74 (s, 1 each, HH′CC(CO₂Me)C′HH′ of each isomer), 2.22 and 2.02 (s, 1 each, HH′CC(CO₂Me)C′HH′ of each isomer), 1.63 and 1.56 (s, 3 each, N═CMe of each isomer), 1.56 and 1.38 (s, 9 each, CMe₃ of each isomer), 1.54 and 1.36 (s, 1 each, HH′CC(CO₂Me)C′HH′ of each isomer).

EXAMPLE 473

Complex 24a. Two equiv (1.10 g, 2.15 mmol) of the sodium salt of the ligand were reacted with one equiv (512 mg, 1.08 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 635 mg (49.5% yield) of a yellow powder: ¹H NMR (CDCl₃) δ 7.72 (s, 1, N═CH), 7.70 (d, 1, Ar′: H), 7.20-7.08 (m, 4, Ar: H, Ar′: H), 3.90 (d, 1, HH′CC(CO₂Me)C′HH′), 3.80 (s, 3, OMe), 3.73 and 2.92 (septet, 1 each, CHMe₂ and C′EMe₂), 2.99 (s, 1, HH′CC(CO₂Me)C′HH′), 2.03 (m, 1, HH′CC(CO₂Me)C′HH′), 1.56 (s, 1, HH′CC(CO₂Me)C′HH′), 1.30, 1.22, 1.08 and 0.93 (d, 3 each, CHMeMe′ and C′HMeMe′).

EXAMPLE 474

Complex 25a. Two equiv (3.25 g, 6.31 mmol) of the sodium salt of the ligand were reacted with one equiv (1.50 g, 3.16 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 3.49 g (90.6% yield) of a yellow powder: ¹H NMR spectrum is clean and consistent with the desired product.

EXAMPLE 475

Complex 26a. Two equiv (2.01 g, 4.20 mmol) of the sodium salt of the ligand were reacted with one equiv (1.00 g, 2.10 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl H₂CC(CO₂Me)CH₂) to give 1.51 g (64.9% yield) of a golden brown powder: ¹H NMR (C₆D₆) δ 7.64 (s, 1, Ar′: H), 7.25 (s, 1, Ar′: H), 6.70 (, 3, Ar: H), 3.85 (s, 1, HH′CC(CO₂Me)C′HH′), 3.15 (s, 3, OMe), 2.44 (s, 1, HH′CC(CO₂Me)CHH′), 1.97 and 1.85 (s, 3 each, Ar: Me, Me′), 1.60 (s, 1, HH′CC(CO₂Me)C′HH′), 1.20 (s, 3, N═CMe), 1.11 (s, 1, HH′CC(CO₂Me)C′HH′); ¹³C NMR (C₆D₆, selected resonances) δ 59.5, 52.7, and 51.3 (H₂CC(CO₂Me)C′H₂), 19.0, 18.6, and 18.0 (N═CMe, Ar: Me, Me′).

EXAMPLE 476

Complex 27a. Two equiv (951 mg, 2.13 mmol) of the sodium salt of the ligand were reacted with one equiv (505 mg, 1.06 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 851 mg (68.6% yield) of a yellow powder: ¹H NMR spectrum in C₆D₆ is clean and consistent with the desired product. The product exists as a 1:1 ratio of isomers (t-Bu group positioned syn or anti to the CC₂Me group.)

EXAMPLE 477

Complex 28a. Two equiv (983 mg, 2.14 mmol) of the sodium salt of the ligand were reacted with one equiv (509 mg, 1.07 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 1.02 g (90.9% yield) of a green powder: ¹H NMR spectrum in C₆D₆ is broad, but consistent with the desired product. The product exists as an ˜1:1 ratio of isomers (t-Bu group positioned syn or anti to the CO₂Me group.)

EXAMPLE 478

Complex 29a. Two equiv (550 mg, 1.59 mmol) of the sodium salt of the ligand were reacted with one equiv (308 mg, 0.647 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 478 mg (64.3% yield) of a dark brown powder.

EXAMPLE 479

Complex 30a. Two equiv (478 mg, 1.27 mmol) of the sodium salt of the ligand were reacted with one equiv (303 mg, 0.637 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 375 mg (61.4% yield) of a dark brown powder:

EXAMPLE 480

Complex 31a. Two equiv (1.04 g, 2.10 mmol) of the sodium salt of the ligand were reacted with one equiv (500 mg, 1.05 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 948 mg (81.1% yield) of a green-yellow powder: ¹H NMR (THF-d₈) δ 7.85, 7.34, 7.14, 7.12, 6.63 and 6.43 (N═CH, H_(aryl), CHPh₂), 3.72 (s, 3, OMe), 3.80, 2.78, 2.78, and 1.48 (s, 1 each, HH′CC(CO₂Me)C′HH′), 1.37 and 1.18 (CMe₃, C′Me₃); ¹³C NMR (THF-d₈) δ 166.9 (N═CH), 167.1, 166.9, 164.1, 142.3, 142.0, 140.9, 135.8, 130.3, 130.0, 129.4, 129.3, 129.27, 128.3, 118.3, 110.4 (C_(aryl) and H₂CC(CO₂Me)CH₂), 81.0 (CHPh2), 59.1 and 45.8 (H₂CC(CO₂Me)CH₂), 52.6 (OMe), 35.9 and 34.3 (CMe₃, C′Me₃), 31.7 and 29.7 (CMe₃, C′Me₃).

EXAMPLE 481

Complex 32a. Two equiv (923 mg, 2.15 mmol) of the sodium salt of the ligand were reacted with one equiv (512 mg, 1.08 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 907 mg (81.1% yield) of a brown-orange powder.

EXAMPLE 482

Complex 33a. Two equiv (891 mg, 2.11 mmol) of the sodium salt of the ligand were reacted with one equiv (502 mg, 1.06 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 940 mg (89.1% yield) of a gold powder. Two major isomers are present in a 1.18:1 ratio. There is a very small amount of a third product or isomer present. The ¹H NMR assignments of the two major isomers follow: ¹H NMR (CDCl₃) δ 8.30 and 8.25 (d, 1 each, Ar′: H of each isomer), 7.48 and 7.32 (d, 1 each, Ar′: H of each isomer), 6.94 and 6.78 (s, 1 each, N═CH of each isomer), 7.05 (m, 2, H_(aryl)), 6.83 (m, 1, H_(aryl)), 6.80 (m, 3, H_(aryl)), 6.58 (d, 1, H_(aryl)), 6.45 (m, 1, H_(aryl)), 3.90 and 3.73 (m, 1 each, HH′CC(CO₂Me)C′HH′ of each isomer), 3.18 and 3.09 (s, 3 each, OMe of each isomer), 2.43 and 2.41 (s, 1 each, HH′CC(CO₂Me)C′HH′ of each isomer), 2.26 and 2.08 (m, 1 each, HH′CC(CO₂Me)C′HH′ of each isomer), 1.30 and 1.17 (s, 1 each, HH′CC(CO₂Me)C′HH′ of each isomer), 1.18 and 1.03 (s, 9 each, CMe₃ of each isomer).

EXAMPLE 483

Complex 34a. Two equiv (719 mg, 1.95 mmol) of the sodium salt of the ligand were reacted with one equiv (464 mg, 0.977 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 928 mg (96.6% yield) of a yellow powder. The ¹H NMR spectrum indicates that two isomers (Cl group positioned syn and anti to the CO₂Me group) are present in a 2.5 to 1 ratio. Major Isomer: ¹H NMR (C₆D₆) δ 8.50 (d, 1, Ar′: H), 7.52 (d, 1, Ar′: H), 7.10 (d, 1, Ar: H), 6.75 (t, 1, Ar: H), 6.72 (s, 1, N═CH), 6.70 (d, 1, Ar: H), 4.02 (d, 1, HH′CC(CO₂Me)C′HH′), 3.28 (s, 3, OMe), 2.60 (s, 1, HH′CC(CO₂Me)C′HH′), 2.18 (d, 1, HH′CC(CO₂Me)C′HH′), 1.99 (s, 3, Ar: Me), 1.63 (s, 1, HH′CC(CO₂Me)C′HH′); Minor Isomer: ¹H NMR (C₆D₆) δ 8.50 (d, 1, Ar′: H), 7.53 (d, 1, Ar′: H), 7.06 (d, 1, Ar: H), 6.8-6.7 (m, 3, N═CH, Ar: H), 4.10 (d, 1, HH′CC(CO₂Me)C′HH′), 3.39 (s, 3, OMe), 2.57 (s, 1, HH′CC(CO₂Me)C′HH′), 2.19 (d, 1, HH′CC(CO₂Me)C′HH′), 1.98 (s, 3, Ar: Me), 1.35 (s, 1, HH′CC(CO₂Me)C′HH′).

EXAMPLE 484

Complex 35a. Two equiv (765 mg, 2.11 mmol) of the sodium salt of the ligand were reacted with one equiv (500 mg, 1.05 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 890 mg (84.7% yield) of a red powder.

EXAMPLE 485

Complex 36a. Two equiv (1.22 g, 2.10 mmol) of the sodium salt of the ligand were reacted with one equiv (500 mg, 1.05 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 1.18 g (81.7% yield) of a yellow powder: ¹H NMR (CD₂Cl₂) δ 8.03 (d, 1, Ar′: H), 7.70 (s, 1, N═CH), 7.36 (d, 1, Ar′: H), 7.20-7.07 (m, 3, Ar: H), 3.88 (m, 1, HH′C(CO₂Me)C′HH′), 3.78 (s, 3, OMe), 3.71 (septet, 1, CHMe₂), 2.97 (s, 1, HH′CC(CO₂Me)C′HH′), 2.90 (septet, 1, C′HMe₂), 1.96 (m, 1, HH′CC(CO₂Me)C′HH′), 1.57 (s, 1 HH″CC(CO₂Me)CHH′), 1.28, 1.20, 1.04 and 0.90 (d, 3 each, CHMeMe′, C′HMeMe′); ¹³C NMR (CD₂Cl₂) δ 166.8 (N═CH), 167.9, 164.6, 153.2, 151.6, 144.4, 141.4, 140.6, 128.4, 125.3, 125.2, 121.1, 114.2, 98.2 and 75.2 (Ar: C_(o), C_(o)′, C_(m), C_(m)′, C_(p); Ar′: C_(o), C_(o)′, C_(m), C_(m)′, C_(p); H₂CC(CO₂Me)C′H₂), 62.7, 54.5 and 50.2 (H₂CC(CO₂Me)C′H₂), 30.2 and 29.8 (CHMe₂, C′HMe₂), 26.7, 26.5, 24.2 and 23.7 (CHMeMe′, C′HMeMe′).

EXAMPLE 486

Complex 37a. Two equiv (771 mg, 2.12 mmol) of the sodium salt of the ligand were reacted with one equiv (504 mg, 1.06 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 992 mg (93.9% yield) of a green powder: ¹H NMR (CD₂Cl₂) δ 8.25 (s, 1, N═CH), 7.18 (m, 3, Ar: H), 6.02 (d, 2, Ar′: H), 5.68 (d, 2, Ar′: H), 3.90 (septet, 1, CHMe₂), 3.84, 3.78 and 3.71 (s, 3 each, Ar: OMe and OMe′; CO₂Me), 3.65 (s, 1, HH′CC(CO₂Me)C′HH′), 3.03 (septet, 1, C′HMe₂), 2.80 (s, 1, HH′CC(CO₂Me)C′HH′), 1.88 (s, 1, HH′CC(CO₂Me)C′HH′), 1.46 (s, 1, HH′CC(CO₂Me)C′HH′), 1.36, 1.28, 1.14 and 0.99 (d, 3 each, CHMeMe′, C′HMeMe′).

EXAMPLE 487

Complex 38a. Two equiv (1.04 g, 2.12 mmol) of the sodium salt of the ligand were reacted with one equiv (503 mg, 1.06 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 1.10 g (89.3% yield) of a green-yellow powder: ¹H NMR (CD₂Cl₂) δ 8.65 (s, 1, N═CH), 7.84 (d, 1, Ar′: H), 7.77 (d, 1, Ar′: H), 7.68 (t, 1, Ar′: H), 7.48 (m, 2, Ar: H), 7.44 (t, 1, Ar′: H), 7.27 (t, 1, Ar′: H), 7.07 (d, 1, Ar′: H), 3.86 (s, 3, OMe), 3.80, 2.84, 2.05 and 1.91 (s, 1 each, HH′CC(CO₂Me) C′HH′).

EXAMPLE 488

Complex 39a. Two equiv (614 mg, 2.10 mmol) of the sodium salt of the ligand were reacted with one equiv (500 mg, 1.05 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 683 mg (77.6% yield) of a green-yellow powder: ¹H NMR (C₆D₆) δ 9.17 (s, 1, N═CH), 8.39 (d, 1, H_(aryl)), 7.62 (d, 1, H_(aryl)), 7.52 (d, 1, H_(aryl)), 7.52 (d, 1, H_(aryl)), 7.44 (d, 1, H_(aryl)), 7.24 (t, 1, H_(aryl)), 7.18 (t, 1, H_(aryl)), 7.11 (d, 1, H_(aryl)), 6.75 (dd, 1, H_(aryl)), 4.19 (br s, 1, HH′CC(CO₂Me)C′HH′), 3.43 (s, 3, OMe), 2.67 (br s, 1, HH′CC(CO₂Me)C′HH′), 2.32 (br s, 1, HH′CC(CO₂Me)C′HH′), 2.24 (s, 3, Ar: Me), 1.65 (s, 1, HH′CC (CO₂Me) C′HH′).

EXAMPLE 489

Compound 40a. Two equiv (765 mg, 2.12 mmol) of the sodium salt of the ligand were reacted with one equiv (505 mg, 1.06 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 925 mg (95.1% yield) of a green powder: Three isomers or products are present in a 1.35 to 1.02 to 1.00 ratio. ¹H NMR (CDCl₃, selected resonances only) δ 8.84, 8.72 and 8.20 (N═CH of the 3 products), 3.29 (OMe of the 3 products—all overlapping), 1.81, 1.45 and 1.25 (CMe₃ of the 3 products).

EXAMPLE 490

Complex 41a. Two equiv (867 mg, 2.22 mmol) of the sodium salt of the ligand were reacted with one equiv (527 mg, 1.11 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 782 mg (77.1% yield) of a golden brown powder: ¹H NMR (C₆D₆) δ 8.08 (d, 2, Ph: C_(o)) 7.27 (m, 6, Ph: C_(m), C_(p); Ar: C_(m), C_(p)), 6.01 (s, 1, PhCCHCMe), 4.23 (s, 1, HH′CC(CO₂Me)C′HH′), 4.03 (septet, 1, CHMe₂), 3.45 (s, 3, OMe), 3.33 (septet, 1, C′HMe₂), 3.04 (s, 1, HH′CC(CO₂Me)C′HH′), 2.18 (s, 1, HH′CC(CO₂Me)CHH′), 1.69 (s, 3, CMeNAr), 1.38 (s, 1, HH′CC(CO₂Me)CHH′), 1.54, 1.41, 1.29 and 1.18 (d, 3 each, CHMeMe′ and C′HMeMe′).

EXAMPLE 491

Complex 42a. Two equiv (495 mg, 2.17 mmol) of the sodium salt of the ligand were reacted with one equiv (516 mg, 1.09 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 434 mg (57.4% yield) of a yellow powder: ¹H NMR (C₆D₆) δ 7.82 (d, 1, H_(aryl)), 7.20 (d, 1, H_(aryl)), 7.10 (t, 1, H_(aryl)), 6.47 (t, 1, H_(aryl)), 4.10 (s, 1, HH′CC(CO₂Me)C′HH′), 3.27 (s, 3, OMe), 3.27 (s, 2, OCH₂, overlaps with OMe), 3.02, 2.73 and 1.11 (s, 1 each, HH′CC(CO₂Me)C′HH′), 0.81 and 0.73 (s, 3 each, CMeMe′).

EXAMPLE 492

Complex 43a. Two equiv (586 mg, 0.909 mmol) of the sodium salt of the ligand were reacted with one equiv (216 mg, 0.455 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 506 mg (74.1% yield) of a dark red powder: ¹H NMR (THF-d₈) δ 7.50 (m, 8, PPh: H_(o)), 7.20 (t, 4, PPh: H_(p)), 7.10 (t, 8, PPh: H_(m)), 6.65 (d, 4, NAr: H_(m)), 6.59 (d, 4, NAr: H_(o)), 3.52 (s, 3, OMe), 2.77 (s, 2, HH′CC(CO₂Me)CHH′), 2.03 (s, 6, NAr: Me), 2.03 or 1.81 (m, 1, PCHP), 1.72 (s, 2, HH′CC(CO₂Me)CHH′); ¹³C NMR (THF-d₈, selected resonances only) δ 50.9 and 47.9 (H₂CC(CO₂Me)CH₂), 19.5 (NAr: Me), 12.0 (t, J_(CP)=109 Hz, PCHP)

EXAMPLE 493

Complex 44a. Two equiv (343 mg, 0.520 mmol) of the sodium salt of the ligand were reacted with one equiv (124 mg, 0.260 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 128 mg (32.8% yield) of an orange powder. The ¹H NMR spectrum is consistent with the presence of one major symmetrical isomer; some of the ligand is also present along with some impurities and possibly the presence of other isomers. (The three possible isomers include the isomer with both methyl groups anti to the CO₂Me group, the isomer with both methyl groups syn to the CO₂Me group, and the isomer with one Me group anti and one Me group syn to the CO₂Me group). The nonaromatic resonances of the major symmetrical isomer follow: ¹H NMR (THF-d₈) δ 3.60 (s, 3, OMe), 2.77 (s, 2, HH′CC(CO₂Me)CHH′), 3.47 or 2.01 (m, 1, PCHP), 1.88 (s, 6, Ar: Me), 1.75 (s, 2, HH′CC(CO₂Me)CHH′).

EXAMPLE 494

Complex 45a. Two equiv (349 mg, 2.10 mmol) of the lithium salt of the ligand were reacted with one equiv (500 mg, 1.05 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 255 mg (40.7% yield) of an brown-yellow powder. ¹H NMR (C₆D₆/THF-d₈) δ 6.02 (s, 1, Thiophene: H), 5.23 (s, 1, Thiophene: H), 3.78 (br s, 1, HH′CC(CO₂Me)C′HH′), 3.40 and 3.38 (s, 3 each, Thiophene: Me and CO₂Me), 2.41 (s, 2, HH′CC(CO₂Me)C′HH′), 2.02 (s, 1, HH′CC(CO₂Me)CHH′).

EXAMPLE 495

Complex 46a. Two equiv (587 mg, 2.11 mmol) of the lithium salt of the ligand were reacted with one equiv (501 mg, 1.05 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 765 mg (84.5% yield) of an orange powder. ¹H NMR spectrum in C₆D₆ is complex. Peaks consistent with two different isomers of the product are present.

EXAMPLE 496

Complex 47a. Two equiv (607 mg, 2.24 mmol) of the sodium salt of the ligand were reacted with one equiv (303 mg, 1.12 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CCHCH₂) to give 482 mg (61.8% yield) of a red powder.

EXAMPLE 497

Complex 48a. Two equiv (149 mg, 1.27 mmol) of the sodium salt of the ligand were reacted with one equiv (302 mg, 0.635 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 146 mg (45.7% yield) of a red powder.

EXAMPLE 498

Complex 49a. Two equiv (700 mg, 2.17 mmol) of the sodium salt of the ligand were reacted with one equiv (515 mg, 1.08 mmol) of [(allyl)Ni(μ-Br)]₂ (allyl=H₂CC(CO₂Me)CH₂) to give 779 mg (685.2% yield) of an orange powder. ¹H NMR spectrum in THF-d₈ is complex.

EXAMPLES 499-503

The following complexes of Examples through were synthesized by mixing the protonated form of the hydroxy-imine ligand with a base (e.g., pyridine, lutidine, acetonitrile, etc.) in an Et₂O solution and cooling this solution to −35° C. The cold Et₂O solution was then added to a cold flask containing (tmeda)NiMe₂. [For the preparation of (tmeda)NiMe₂ please see: Kaschube, W.; Porschke, K. R.; Wilke, G. J. Organomet. Chem. 1988, 355, 525-532.] The reaction mixture was stirred for ˜4 h. The solution was then filtered though a frit with dry Celite®. The solvent was removed and the product was dried in vacuo.

EXAMPLE 499

Complex 50. One equiv of [2-(OH)-3,5-Cl₂—C₆H₂—C(Me)═NAr [Ar=2,6-(i-Pr)₂—C₆H₃] (356 mg, 0.976 mmol) was reacted with (tmeda)NiMe₂ (200 mg, 0.976 mmol) and pyridine (772 mg, 9.76 mmol) to yield an orange-red powder: ¹H NMR (C₆D₆) δ 8.66 (d, 2, Py: H_(o)), 7.50 (d, 1, Ar′: H), 7.31 (d, 1, Ar′: H), 7.09 (m, 3, Ar: H), 6.63 (t, 1, Py: H_(p)), 6.29 (t, 1, Py: H_(m)), 3.98 (septet, 2, CHMe₂), 1.68 (d, 6, CHMeMe′), 1.51 (s, 3, N═CMe), 1.04 (d, 6, CHMeMe′), −0.92 (s, 3, NiMe).

EXAMPLE 500

Complex 51. One equiv of [2-(OH)-3,5-Cl₂—C₆H₂—C(Me)═NAr [Ar=2,6-(i-Pr)₂—C₆H₃] (88.8 mg, 0.244 mmol) was reacted with (tmeda)NiMe₂ (50 mg, 0.244 mmol) and lutidine (26.2 mg, 0.244 mmol) to yield an orange powder: ¹H NMR (C₆D₆) δ 7.35 (d, 1, Ar′: H), 7.28 (d, 1, Ar′: H), 7.01 (s, 3, Ar: H), 6.64 (t, 1, Lutidine: H_(p)), 6.28 (d, 2, Lutidine: H_(m)), 3.91 (septet, 2, CHMe₂), 3.72 (s, 6, Lutidine: Me), 1.52 (d, 6, CHMeMe′), 1.46 (s, 3, N═CMe), 0.98 (d, 6, CHMeMe′), −1.42 (s, 3, NiMe).

EXAMPLE 501

Complex 52. One equiv of [2-(OH)-3,5-Cl₂—C₆H₂—C(Me)═NAr [Ar=2,6-(i-Pr)₂-C₆H₃] (370 mg, 1.02 mmol) was reacted with (tmeda)NiMe₂ (209 mg, 1.02 mmol) and acetonitrile (10 mL) to yield a yellow-orange powder: ¹H NMR (CD₂Cl₂) δ 7.23 (d, 1, Ar′: H), 7.10 (t, 1, Ar: H_(p)), 7.04 (d, 2, Ar: H_(m)), 6.95 (d, 1, Ar′: H), 4.34 (septet, 2, CHMe₂), 1.89 (s, 3, N═CMe), 1.70 (s, 3, NC≡Me), 1.33 (d, 6, CHMeMe′), 1.15 (d, 6, CHMeMe′), 0.80 (s, 3, NiMe)

EXAMPLE 502

Complex 53. One equiv of [2-(OH)-3,5-Cl₂—C₆H₂—C(Me)═NAr [Ar=2,6-(i-Pr)₂—C₆H₃] (88.8 mg, 0.244 mmol) was reacted with (tmeda)NiMe₂ (50 mg, 0.244 mmol) and p-tolunitrile (28.6 mg, 0.244 mmol) to yield a brown powder: ¹H NMR (CD₂Cl₂) δ 7.74 (d, 2, Nitrile: H), 7.23 (d, 1, Ar′: H), 7.21 (d, 2, Nitrile: H), 7.10 (t, 1, Ar: H_(p)), 7.04 (d, 1, Ar: H_(m)), 6.95 (d, 1, Ar′: H), 4.34 (septet, 2, CHMe₂), 2.33 (s, 3, Nitrile: Me), 1.70 (s, 3, N═CMe), 1.33 (d, 6, CHMeMe′), 1.15 (d, 6, CHMeMe′), 0.80 (s, 3, NiMe).

EXAMPLE 503

Complex 54. One equiv of [2-(OH)-3,5-Br₂—C₆H₂—C(Me)═NAr [Ar=2,6-(i-Pr)₂—C₆H₃] (111 mg, 0.244 mmol) was reacted with (tmeda)NiMe₂ (50 mg, 0.244 mmol) and pyridine (200 mg) to yield a yellow-orange powder: ¹H NMR (C₆D₆) δ 8.77 (d, 2, Py: H_(o)), 7.60 (t, 1, Py: H_(p)), 7.52 (d, 1, Ar′: H), 7.44 (d, 1, Ar′: H), 7.13 (t, 2, Py: H_(m)), 7.10 (s, 3, Ar: H), 3.85 (septet, 2, ChMe₂), 1.82 (s, 3, N═CMe), 1.51 (d, 6, CHMeMe′), 1.07 (d, 6, CHMeMe′), −1.42 (s, 3, NiMe).

EXAMPLES 504-509 General Procedure for Ethylene(28-35 kPa)/α-Olefin Copolymerizations of Table 19

In the drybox, a glass Schlenk flask was loaded with the nickel compound, Lewis acid, solvent, comonomer, and a stir bar. The flask was then capped with a rubber septum and the stopcock was closed prior to removing the flask from the drybox. The flask was then attached to the ethylene line where it was evacuated and backfilled with ethylene. The reaction mixture was stirred under ethylene for the stated reaction time, the ethylene pressure was then released, and the polymer was precipitated by adding the reaction mixture to a solution of MeOH (˜100 mL) and concentrated HCl (˜1-3 mL). The solid polymer was then collected on a frit and rinsed with MeOH. For amorphous polymers, the MeOH was decanted off of the polymer. Often, the amorphous polymer was dissolved in hexane and reprecipitated in methanol. The polymer was transferred to a pre-weighed vial and dried under vacuum overnight. The polymer yield and characterization were then obtained.

For Example 505 the following quantitative ¹³C NMR (TCB, 120-140° C.) was obtained: Branching per 1000 CH₂'s; total methyls (98.4), methyl (54.5), ethyl (13.1), propyl (3.2), butyl (14.4), amyl (4.9), hexyl and greater and end of chains (11.1), amyl and greater and end of chains (13.7), butyl and greater and end of chains (27.6)

For Example 506 the following quantitative ¹³C NMR (TCB, 120-140° C.) was obtained: Branching per 1000 CH₂'s; total methyls (115.4), methyl (61.5), ethyl 12.8), propyl (3.8), butyl (21.3), amyl (4.0), hexyl and greater and end of chains (14.4), amyl and greater and end of chains (16.3), butyl and greater and end of chains (37.2)

TABLE 19 Ethylene/α-Olefin Copolymerizations at 28-35 kPa Ethylene Lewis Acid Time Toluene Comonomer Polymer Ex. Cmpd (equiv) (h) (mL) (mL) (g) 504 3a BPh₃/20 32 30 1-Hexene (10)  0.633 Description: Viscous clear oil. ¹H NMR (C₆D₆, rt): 198.2 Total Me/1000 CH₂ 505 6a B(C₆F₅)₃/20 24.2 30 1-Hexene (5) 7.31 Description: Tough, rubbery, amorphous light tan solid. ¹H NMR (C₆D₆, rt): 116.1 Total Me/1000 CH₂ 506 6a B(C₆F₅)₃/20 24.2 25 1-Hexene (10) 6.26 Description: Rubbery, slightly sticky amorphous light tan solid. ¹H NMR (C₆D₆, rt): 129.9 Total Me/1000 CH₂ 507 6a B(C₆F₅)₃/20 24.2 20 1-Hexene (15) 4.18 Description: Sticky, very viscous oil--almost a solid. ¹H NMR (C₆D₆, rt): 167.9 Total Me/1000 CH₂ 508 6a B(C₆F₅)₃/20 33.3 30 1-Octene (5) 5.65 Description: Tough, amorphous rubbery solid. ¹H NMR (C₆D₆, rt): 112.0 Total Me/1000 CH₂ 509 9a B(C₆F₅)₃/20 27.3 30 1-Octene (5) 7.53 Description: Sticky, amorphous light tan solid. ¹H NMR (C₆D₆, rt): 178.7 Me/1000 CH₂

EXAMPLES 510-512 General Procedure for Homopolymerizations of 1-Hexene, 1-Octene, and Cyclopentene by Cmpd 6a (Table 20)

In the drybox, the nickel compound, Lewis acid, solvent, monomer and stir bar were placed together in a round bottom flask. The reaction mixture was stirred for the stated amount of time. The flask was removed from the drybox and water and concentrated hydrochloric acid were added. The product was extracted with toluene and/or hexane and the solution was filtered through a frit containing a layer of neutral alumina on top of a layer of silica gel. The solvent was then evaporated and the product was dried in vacuo.

TABLE 20 Ethylene/α-Olefin Copolymerizations at 28-35 kPa Ethylene Poly- Lewis Acid Time Toluene Comonomer mer Ex. Cmpd (equiv) (weeks) (mL) (mL) (g) 510 6a B(C₆F₅)₃/20 ˜2 5 1-Hexene (10) 0.511 Description: Viscous oil. ¹H NMR (C₆D₆, rt): 152.2 Total Me per 1000 Carbon Atoms; DP˜17.4; M_(n)˜1,460 511 6a B(C₆F₅)₃/20 ˜2 5 1-Octene (10) 1.83  Description: Free-flowing, slightly viscous oil. ¹H NMR (C₆D₆, rt): 122.8 Total Me per 1000 Carbon Atoms; DP˜10.5; M_(n)˜1,180 512 6a B(C₆F₅)₃/20 ˜2 5 Cyclopentene 1.57  (10) Description: Partial viscous oil/partial solid. ¹H NMR (C₆D₆) indicates polycyclopentene formation with olefinic end groups present. 

What is claimed is:
 1. A compound of the formula:

wherein: A is a π-allyl or π-benzyl group; L¹ is a neutral monodentate ligand which may be displaced by an olefin, and L² is a monoanionic monodentate ligand, or L¹ and L² taken together are a monoanionic bidentate ligand, provided that said monoanionic monodentate ligand or said monoanionic bidentate ligand may add to said olefin; Ar¹, Ar², Ar⁴, Ar⁵, Ar¹⁰, Ar¹¹, Ar¹² and Ar¹³ are each independently aryl or substituted aryl; R¹ and R² are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R¹ and R² taken together form a ring, and R³ is hydrogen, hydrocarbyl or substituted hydrocarbyl or R¹, R² and R³ taken together form a ring; R¹⁰ and R¹⁵ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; R¹¹, R¹², R¹³, R¹⁴, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R⁵⁰, R⁵¹, R⁵², R⁵³ and R⁵⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group, and provided that any two of these groups vicinal to one another taken together may form a ring; K is N or CR²⁷; R²² is hydrocarbyl, substituted hydrocarbyl, —SR¹¹⁷, —OR¹¹⁷, or —NR¹¹⁸ ₂, R²⁴ is hydrogen, a functional group, hydrocarbyl or substituted hydrocarbyl, and R²⁷ is hydrocarbyl or substituted hydrocarbyl, and provided that R²² and R²⁴ or R²⁴ and R²⁷ taken together may form a ring; R¹¹⁷ is hydrocarbyl or substituted hydrocarbyl; each R¹¹⁸ is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; G and L are both N or G is CR⁵⁷ and L is CR⁵⁵; R⁵⁵, R⁵⁶ and R⁵⁷ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or any two of R⁵⁵, R⁵⁶ and R⁵⁷ taken together form a ring; R⁷⁸ is hydrocarbyl or substituted hydrocarbyl; R⁷⁹, R⁸⁰, R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸ and R⁸⁹ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group; R⁹⁰, R⁹¹, R⁹² and R⁹³ are each independently hydrocarbyl or substituted hydrocarbyl; R⁹⁴ and R⁹⁵ are each independently hydrocarbyl or substituted hydrocarbyl; R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group; both of T are S (sulfur) or NH (amino); each E is N (nitrogen) or CR¹⁰⁸ wherein R¹⁰⁸ is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group; R¹⁰⁰, R¹⁰¹, R¹⁰², R¹⁰³, R¹⁰⁴, R¹⁰⁵, R¹⁰⁶, and R¹⁰⁷ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group; R¹⁰⁹, R¹¹⁰, R¹¹¹, R¹¹², R¹¹³, R¹¹⁴, R¹¹⁵ and R¹¹⁶ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group; and R²⁸ and R²⁹ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl.
 2. The compound as recited in claim 1 which is (I) or (VII).
 3. The compound as recited in claim 2 wherein: R¹ and R² are both hydrogen; R³ is alkyl or aryl containing 1 to 20 carbon atoms, or R¹, R² and R³ taken together are

Ar¹ and Ar² are each independently

 wherein R³⁶, R³⁷, R³⁸, R³⁹ and R⁴⁰ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any 2 of R³⁶, R³⁷, R³⁸, R³⁹ and R⁴⁰ that are vicinal to one another taken together may form a ring.
 4. The compound as recited in claim 3 wherein R³ is t-butyl, R¹ and R² are hydrogen, and R³⁶ and R³⁹ are halo, phenyl, or alkyl containing 1 to 6 carbon atoms.
 5. The compound as recited in claim 1 which is (II) or (VIII).
 6. The compound as recited in claim 5 wherein: R¹⁰ is hydrogen or methyl; R⁷⁸ is Ar³, which is aryl or substituted aryl; and R¹¹, R¹², R¹³ and R¹⁴ are each independently chloro, bromo, iodo, alkyl, alkoxy, hydrogen or nitro, or R¹¹ and R¹² taken together form a 6-membered carbocyclic ring and R¹³ and R¹⁴ are hydrogen.
 7. The compound as recited in claim 1 which is (III) or (IX).
 8. The compound as recited in claim 7 wherein: R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are hydrogen; and Ar⁴ is

 wherein R³⁶, R³⁷, R³⁸, R³⁹ and R⁴⁰ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any 2 of R³⁶, R³⁷, R³⁸, R³⁹ and R⁴⁰ that are vicinal to one another taken together may form a ring.
 9. The compound as recited in claim 1 which is (IV) or (X).
 10. The compound as recited in claim 9 wherein R¹⁹, R²⁰ and R²¹ are hydrogen, or R¹⁹ and R²⁰ are hydrogen and R²¹ is methyl.
 11. The compound as recited in claim 1 which is (V) or (XI).
 12. The compound as recited in claim 11 wherein: K is CR²⁷; R²⁷ is hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group; R²⁴ is hydrogen, alkyl or halo; R²² is hydrocarbyl or —OR¹¹⁷, wherein R¹¹⁷ is hydrocarbyl.
 13. The compound as recited in claim 12 wherein: R²⁷ is methyl; R²² is phenyl, or —OR¹¹⁷, R¹¹⁷ is alkyl containing 1 to 6 carbon atoms; and R²⁴ is hydrogen.
 14. The compound as recited in claim 1 which is (VI) or (XII).
 15. The compound as recited in claim 14 wherein: R³² and R³³ are both alkyl containing 1 to 6 carbon atoms or phenyl, more preferably isopropyl, R²⁸ and R²⁹ are both hydrogen or phenyl, and R³⁰, R³¹, R³⁴ and R³⁵ are all hydrogen; or R³¹ and R³² taken together and R³³ and R³⁴ taken together are both a 6-membered aromatic carbocyclic ring having a t-butyl group vicinal to the R³² and R³³ positions, and R²⁸ and R²⁹ are both hydrogen.
 16. The compound as recited in claim 1 which is (XVIII) or (XIX).
 17. The compound as recited in claim 16 wherein: R⁵⁰, R⁵¹, R⁵², R⁵³ and R⁵⁴ are hydrogen; and Ar¹⁰ and Ar¹¹ are each independently

 wherein R³⁶, R³⁷, R³⁸, R³⁹ and R⁴⁰ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any 2 of R³⁶, R³⁷, R³⁸, R³⁹ and R⁴⁰ that are vicinal to one another taken together may form a ring.
 18. The compound as recited in claim 1 which is (XXVII) or (XXVIII).
 19. The compound as recited in claim 18 wherein: L is CR⁵⁵; R⁵⁵ is hydrocarbyl, hydrogen, or substituted hydrocarbyl; G is CR⁵⁷; R⁵⁷ is hydrocarbyl, hydrogen or substituted hydrocarbyl; R⁵⁶ is hydrogen; and Ar¹² and Ar¹³ are each independently

 wherein R³⁶, R³⁷, R³⁸, R³⁹ and R⁴⁰ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any 2 of R³⁶, R³⁷, R³⁸, R³⁹ and R⁴⁰ that are vicinal to one another taken together may form a ring.
 20. The compound as recited in claim 19 wherein R⁵⁵ and R⁵⁷ are both alkyl or fluorinated alkyl, and Ar¹² and Ar¹³ are both 2,6-diisopropylphenyl.
 21. The compound as described in claim 1 which is (XXXVII) or (XXXXI).
 22. The compound as recited in claim 21 wherein: R⁷⁹, R⁸⁰, R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸ and R⁸⁹ are each independently hydrogen or alkyl; and R⁹⁰, R⁹¹, R⁹² and R⁹³ are each independently hydrocarbyl.
 23. The compound as described in claim 1 which is (XXXVIII) or (XXXXII).
 24. The compound as recited in claim 23 wherein: R⁹⁴ and R⁹⁵ are each independently hydrocarbyl; and R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹ are each independently hydrogen or hydrocarbyl.
 25. The compound as recited in claim 1 which is (XXXIX) or (XXXXIII).
 26. The compound as recited in claim 25 wherein: E is N or CR¹⁰⁸; R¹⁰⁸ is hydrogen or hydrocarbyl; and R¹⁰⁰, R¹⁰¹, R¹⁰², R¹⁰³, R¹⁰⁴, R¹⁰⁵, R¹⁰⁶, and R¹⁰⁷ each independently hydrogen, hydrocarbyl, or halo.
 27. The compound as recited in claim 1 which is (XXXX) or (XXXXIV).
 28. The compound as recited in claim 27 wherein R¹⁰⁹, R¹¹⁰, R¹¹¹, R¹¹², R¹¹³, R¹¹⁴, R¹¹⁵, R¹¹⁶ are each independently hydrogen or hydrocarbyl.
 29. The compound as recited in claim 1 wherein L¹ is a nitrile, pyridine, or a substituted pyridine, and L² is methyl.
 30. The compound as recited in claim 1 wherein L¹ and L² taken together are not π-allyl or π-benzyl.
 31. A compound of the formula

wherein: R⁵⁸, R⁵⁹, R⁶⁰, R⁶², R⁶³ and R⁶⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group, and provided that any two of these groups vicinal to one another taken together may form a ring, or if vicinal to R⁶¹ or R⁶⁵ form a ring with them; R⁶⁶ is hydrogen, hydrocarbyl or substituted hydrocarbyl; and R⁶¹ and R⁶⁵ are each independently hydrocarbyl containing 2 or more carbon atoms, or substituted hydrocarbyl containing 2 or more carbon atoms, and provided that R⁶¹ and R⁶⁵ may form a ring with any group vicinal to it.
 32. The compound as recited in claim 29 wherein; R⁵⁸, R⁵⁹, and R⁶⁰ are hydrogen; R⁶⁶ is hydrogen; R⁶¹ and R⁶⁵ are each independently alkyl containing 2 or more carbon atoms; and R⁶², R⁶³ and R⁶⁴ are hydrogen.
 33. A compound of the formula

wherein: R⁶⁶ is hydrocarbyl, substituted hydrocarbyl, —SR¹¹⁷, —OR¹¹⁷, or —NR¹¹⁸ ₂, R⁷⁶ is hydrogen, a functional group, hydrocarbyl or substituted hydrocarbyl, and R⁷⁵ is hydrocarbyl or substituted hydrocarbyl, and provided that R⁶⁸ and R⁷⁶ or R⁷⁵ and R⁷⁶ taken together may form a ring; R¹¹⁷ is hydrocarbyl or substituted hydrocarbyl; each R¹¹⁸ is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; R⁷⁰, R⁷¹ and R⁷² are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group; R⁶⁹ and R⁷³ are hydrocarbyl containing 3 or more carbon atoms, substituted hydrocarbyl containing 3 or more carbon atoms or a functional group; and provided that any two of R⁷⁰, R⁷¹, R⁷², R⁶⁹ and R⁷³ vicinal to one another together may form a ring.
 34. The compound as recited in claim 33 wherein: R⁶⁸ is —OR¹¹⁷ or aryl; R⁷⁵ is hydrocarbyl or substituted hydrocarbyl; and R⁷⁶ is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group.
 35. The compound as recited in claim 34 wherein R⁷⁶ is hydrogen, hydrocarbyl or substituted hydrocarbyl. 